KR100533933B1 - Solid electrolyte and a method for preparing the same - Google Patents
Solid electrolyte and a method for preparing the same Download PDFInfo
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- KR100533933B1 KR100533933B1 KR10-2002-0032041A KR20020032041A KR100533933B1 KR 100533933 B1 KR100533933 B1 KR 100533933B1 KR 20020032041 A KR20020032041 A KR 20020032041A KR 100533933 B1 KR100533933 B1 KR 100533933B1
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title description 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- 239000010409 thin film Substances 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- -1 B 2 O 3 Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910008373 Li-Si-O Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910008291 Li—B—O Inorganic materials 0.000 description 1
- 229910006711 Li—P—O Inorganic materials 0.000 description 1
- 229910006757 Li—Si—O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
-
- 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
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- 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)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
본 발명은 고체 전해질 및 그 제조 방법에 관한 것으로서, 본 발명의 고체 전해질은 Li, X, Y, Z, O 및 N(여기서, X, Y 및 Z는 각각 P, B, Si, Al, Ge 및 As로 이루어진 군에서 선택됨)의 6 개의 원자를 함유하는 6 원계 박막 전지용 전해질이다. 상기 X, Y 및 Z는 네트워크의 골격을 형성하는 물질이고, N은 네트워크의 골격을 개질시켜 그물 구조를 형성하는 물질이다. The present invention relates to a solid electrolyte and a method for producing the same, wherein the solid electrolyte of the present invention is Li, X, Y, Z, O and N (where X, Y and Z are P, B, Si, Al, Ge and It is a 6-membered thin film electrolyte containing 6 atoms of) selected from the group consisting of As. X, Y, and Z are substances that form a skeleton of the network, and N is a substance that forms a net structure by modifying the skeleton of the network.
Description
[산업상 이용분야][Industrial use]
본 발명은 고체 전해질 및 그 제조 방법에 관한 것으로서, 보다 구체적으로는, 세개 이상의 네트워크 형성제를 갖는 고체 박막 전해질 및 그 제조 방법에 관한 것이다. The present invention relates to a solid electrolyte and a method for producing the same, and more particularly, to a solid thin film electrolyte having three or more network formers and a method for producing the same.
[종래기술][Private Technology]
화학적 에너지를 전기적 에너지로 변화시키는 전지는 에너지 변환 효율이 높고 간편한 구조로 인해 널리 사용되어 왔다. 그 중에서 리튬 전지는 높은 전위를 가지며, 에너지 밀도가 높으므로 인해 오늘날 전지 분야에서 가장 연구가 활발히 진행되고 있는 것 중의 하나이다.Batteries that convert chemical energy into electrical energy have been widely used due to their high energy conversion efficiency and simple structure. Among them, lithium batteries have high potential and high energy density, which is one of the most active researches in the field of batteries today.
이러한 리튬 전지는 기본적으로 음극(예: 리튬 금속, 리튬 합금, 및 리튬을 탈 삽입시킬 수 있는 흑연), 양극(예: LiCoO2, Li2MnO4 및 V2O 5) 및 전해질로 구성되어 있다. 그 중에서 오늘날 전지의 성능과 가장 밀접한 관계를 가지고 있는 것은 리튬 이온의 이동 통로를 제공하는 전해질이다.These lithium batteries are basically composed of a negative electrode (e.g. lithium metal, a lithium alloy, and graphite capable of deintercalating lithium), a positive electrode (e.g. LiCoO 2 , Li 2 MnO 4 and V 2 O 5 ), and an electrolyte. . One of the most closely related to the performance of the battery today is the electrolyte that provides the passage of lithium ions.
리튬 전지용 전해질의 예로는 액체 전해질 및 고체 전해질을 들 수 있다. 액체 전해질은 종래 리튬 전지에 널리 사용된 전해질로서, 높은 이온 전도도를 나타낸다는 장점을 가지고 있다. 그러나, 이것은 기본적으로 산 용액으로서 환경적으로 바람직하지 못하며 누수에 따른 위험성을 내포하고 있다는 문제점을 안고 있다. 이러한 문제점을 해결하고자 제시된 것이 고체 전해질이며, 이것은 크게 고체 고분자 전해질과 고체 박막 전해질로 대별할 수 있다.Examples of electrolytes for lithium batteries include liquid electrolytes and solid electrolytes. The liquid electrolyte is an electrolyte widely used in a conventional lithium battery and has an advantage of exhibiting high ionic conductivity. However, this is basically an acid solution, which is environmentally undesirable and poses a problem of leakage. In order to solve this problem, a solid electrolyte is proposed, which can be roughly classified into a solid polymer electrolyte and a solid thin film electrolyte.
고체 고분자 전해질은 폴리에틸렌옥사이드(PEO)로 이루어진 고분자 매트릭스가 리튬 이온에 대한 전도성을 갖는다는 발견에 기초하여, 현재 폴리아크릴로니트릴(PAN), 폴리비닐클로라이드(PVC)등과 같은 다양한 조성의 고분자 전해질이 개발 중에 있다. Solid polymer electrolytes are based on the discovery that a polymer matrix composed of polyethylene oxide (PEO) has conductivity to lithium ions. It is under development.
그러나 이러한 고체 고분자 전해질은 기본적으로 벌크 전지에 사용되는 것을 전제한 것으로서, 전체 전지의 크기가 수 ㎛에 불과한 박막 전지용 전해질로는 그 사용이 제한되어 있다. 고체 박막 전해질은 새롭게 각광 받고 있는 박막 전지용 전해질로서, 네트워크의 골격을 형성하는 네트워크 형성제 및 네트워크의 골격을 개질시키는 네트워크 개질제(network modifier)를 기본적으로 포함하고, 추가로 네트워크에 리튬이온의 첨가량을 증진시키는 네트워크 도핑제(network dopant)를 포함할 수 있다. 이러한 고체 박막 전해질의 대표적 예로는 Li-P-O-N을 구성 요소로 포함하고 있는 미국 특허 제5,338,625호 및 그의 분할 출원인 미국 특허 제5,455,126호를 들 수 있다.However, such a solid polymer electrolyte is basically assumed to be used in a bulk battery, and its use is limited to an electrolyte for a thin film battery having a total size of only a few μm. Solid-state thin film electrolytes are emerging as electrolytes for thin-film batteries, and basically include network modifiers that form the backbone of the network and network modifiers that modify the backbone of the network, and further add lithium ions to the network. May include a network dopant to enhance. Representative examples of such solid thin film electrolytes include U.S. Patent No. 5,338,625, which includes Li-P-O-N as a component, and U.S. Patent No. 5,455,126, which is a divided application thereof.
상기 미국 특허의 고체 박막 전해질은 네트워크의 골격을 형성하는 네트워크 형성제로 Li-P-O를 갖고, 네트워크 골격의 절단, 축중합, 브랜칭(branching)등에 의해 네트워크의 골격을 개질시켜 그물구조를 형성하는 네트워크 개질제(network modifier)로 N을 갖고 있다.The solid film electrolyte of the US patent has a network forming agent for forming a network skeleton, and has a Li-PO, and a network modifier for forming a net structure by modifying the network skeleton by cutting, condensation polymerization, and branching the network skeleton. has N as its (network modifier).
그러나, 상기의 미국 특허에도 불구하고, 고체 박막 전해질에 대한 개발은 아직 초기 단계에 머무르고 있으며, 보다 우수한 전지 성능을 제공할 수 있는 다양한 형태의 고분자 옥사이드 전해질의 개발이 요청되고 있는 실정이다.However, despite the above-mentioned US patent, the development of a solid thin film electrolyte is still in its infancy, and there is a demand for the development of various types of polymer oxide electrolytes that can provide better battery performance.
상기 문제점을 해결하기 위하여 안출된 것으로서, 본 발명의 목적은 새로운 고체 박막 전해질을 제공하는 것이다.In order to solve the above problems, an object of the present invention is to provide a new solid thin film electrolyte.
본 발명의 다른 목적은 세 개 이상의 네트워크 형성제를 가지는 6 원계 고체 전해질을 제공하는 것이다.Another object of the present invention is to provide a six-membered solid electrolyte having three or more network formers.
본 발명의 또 다른 목적은 상기 고체 전해질을 제조하는 방법을 제공하는 것이다.Still another object of the present invention is to provide a method for preparing the solid electrolyte.
상기한 본 발명의 목적 및 다른 목적들은 전해질 구성 원소 간의 물성을 제어하여 구성 성분들간의 결합력과 결합 구조를 변화시켜, 높은 리튬 이온 전도도, 낮은 전자 전도도 및 구조적으로 안정한 그물 구조를 형성하여 전극과 계면에서 안정한 전해질을 제공함에 의해 성취될 수 있다.The above and other objects of the present invention control the physical properties between the electrolyte components to change the bonding force and bonding structure between the components, forming a high lithium ion conductivity, low electron conductivity and structurally stable net structure to interface with the electrode It can be achieved by providing a stable electrolyte at.
본 발명은 상기한 목적을 달성하기 위하여, Li, X, Y, Z, O 및 N(여기서, X, Y 및 Z는 각각 P, B, Si, Al, Ge 및 As로 이루어진 군에서 선택됨)의 6개의 원자를 함유하는 6원계 고체 전해질을 제공한다.The present invention, in order to achieve the above object, of Li, X, Y, Z, O and N (where X, Y and Z are each selected from the group consisting of P, B, Si, Al, Ge and As) A six-membered solid electrolyte containing six atoms is provided.
본 발명은 또한 Li, X, Y, Z, 및 O(여기서, X, Y 및 Z는 각각 P, B, Si, Al, Ge 및 As로 이루어진 군에서 선택됨)를 제공할 수 있는 타겟을 형성하고; 순수한 N2 또는 N2를 포함하는 분위기 하에서 스퍼터링을 수행하여 Li, X, Y, Z, O 및 N의 6 개의 원소를 함유하는 박막을 형성하는 단계를 포함하는 Li, X, Y, Z, O 및 N의 6개의 원자를 함유하는 6원계 고체 전해질의 제조방법을 제공한다.The present invention also forms a target capable of providing Li, X, Y, Z, and O, wherein X, Y and Z are each selected from the group consisting of P, B, Si, Al, Ge and As. ; Li, X, Y, Z, O comprising the step of sputtering under an atmosphere containing pure N 2 or N 2 to form a thin film containing six elements of Li, X, Y, Z, O and N And a six-membered solid electrolyte containing six atoms of N.
이하 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 박막 전지용 고체 전해질에 관한 것으로서, 상기 고체 전해질은 Li, X, Y, Z, 및 O(여기서, X, Y 및 Z는 각각 P, B, Si, Al, Ge 및 As로 이루어진 군에서 선택됨)의 6개의 원자를 함유하는 6원계 고체 박막 전해질이다.The present invention relates to a solid electrolyte for a thin film battery, wherein the solid electrolyte is Li, X, Y, Z, and O (where X, Y, and Z are each P, B, Si, Al, Ge, and As in the group consisting of). 6-membered solid thin film electrolyte.
본 발명의 고체 전해질은 세개 이상의 네트워크 형성제인 X, Y 및 Z를 포함한다. 본 발명의 6원계 고체 전해질의 구성 원소중 X, Y 및 Z는 네트워크의 골격을 형성하는 물질이고, N은 네트워크의 골격을 개질시켜 그물 구조를 형성하는 물질이다. The solid electrolyte of the present invention comprises at least three network formers X, Y and Z. Among the constituent elements of the six-membered solid electrolyte of the present invention, X, Y and Z are substances forming a skeleton of the network, and N is a substance modifying the skeleton of the network to form a net structure.
네트워크의 골격을 형성하는 B, Si, 및 P인 경우 각각 B2O3, SiO2, P2 O5 등의 화합물에 의해 공급될 수 있다. 네트워크의 골격을 개질시켜 그물 구조를 형성하는 물질(N)은 Li3N 등의 화합물에 의해 공급될 수 있다.In the case of B, Si, and P forming the skeleton of the network, they may be supplied by compounds such as B 2 O 3 , SiO 2 , P 2 O 5, and the like. The substance (N) for modifying the skeleton of the network to form a net structure can be supplied by a compound such as Li 3 N.
본 발명의 Li, X, Y, Z, O 및 N(여기서, X, Y 및 Z는 각각 P, B, Si, Al, Ge 및 As로 이루어진 군에서 선택됨)의 6개의 원자를 함유하는 6원계 고체 전해질은 Li, X, Y, Z, 및 O를 제공할 수 있는 타겟을 형성하고; 순수한 N2 또는 N2를 포함하는 분위기 하에서 스퍼터링을 수행하여 Li, X, Y, Z, O 및 N의 6 개의 원소를 함유하는 박막을 형성하는 단계를 포함하는 공정에 의해서 제조된다.Hexane system containing six atoms of Li, X, Y, Z, O and N of the present invention, wherein X, Y and Z are each selected from the group consisting of P, B, Si, Al, Ge and As The solid electrolyte forms a target capable of providing Li, X, Y, Z, and O; Sputtering under an atmosphere containing pure N 2 or N 2 to form a thin film containing six elements of Li, X, Y, Z, O and N.
Li, X, Y, Z, 및 O를 제공할 수 있는 타겟으로는 Li, X, 및 O를 함유하는 화합물의 타겟 위에 Y 또는 Y-함유 화합물 및 Z 또는 Z-함유 화합물의 모자이크 타겟을 위치시킨 타겟을 사용할 수도 있고, 또한 Li, X, Y, Z, 및 O 원소를 함유하는 복합 타겟을 사용할 수도 있으나 이들 방법에 한정되는 것은 아니다. 복합 타겟을 이용하는 경우 Li2B4O7 : Li2SiO3 : Li3PO 4 복합 타겟이 이용될 수 있다.Targets that can provide Li, X, Y, Z, and O include a mosaic target of a Y or Y-containing compound and a Z or Z-containing compound over a target of a compound containing Li, X, and O. The target may be used, or a composite target containing Li, X, Y, Z, and O elements may be used, but is not limited to these methods. When a composite target is used, a Li 2 B 4 O 7 : Li 2 SiO 3 : Li 3 PO 4 composite target may be used.
본 발명의 바람직한 구체예에 따르면, Li-B-O, Li-Si-O, 및 Li-P-O의 세 개의 네트워크 형성제를 갖고, N을 네트워크 개질제로 갖는 6 원계 전해질이 제공된다. According to a preferred embodiment of the present invention, a six-membered electrolyte having three network formers of Li-B-O, Li-Si-O, and Li-P-O and having N as a network modifier is provided.
상기 고체 전해질을 제조하는 방법은 Li, B, Si, P, 및 O를 제공할 수 있는 타겟을 형성하고; 순수한 N2 또는 N2를 포함하는 분위기 하에서 스퍼터링을 수행하여 Li, B, Si, P, O 및 N의 6 개의 원소를 함유하는 박막을 형성하는 단계를 포함한다.The method of making the solid electrolyte comprises forming a target capable of providing Li, B, Si, P, and O; Sputtering under an atmosphere containing pure N 2 or N 2 to form a thin film containing six elements of Li, B, Si, P, O and N.
본 발명에 따른 전해질은 저온 공정에 의해 비정질 형태를 유지하며, 이것에 의해 높은 전하 이동체(charge carrier)농도, 높은 베이컨시(vacancy) 또는 틈새 자리(interstitial site)농도, 낮은 이온 이동 활성화 에너지에 의해 높은 이온 전도도를 갖는다. 본 발명의 전해질은 Li-B-O에 첨가된 Si, P 및 N 물질이 네트워크의 구조적 안정화에 기여하여, 각 원소간의 결합력, 결합 특성, 결합의 상대적 강도, 리튬 이온과의 반응성을 향상시켜 구조적 및 화학적으로 안정한 특성을 나타낸다. 따라서, 상기의 전해질은 박막 전지 뿐만 아니라 초소형 센서, 의료기기, 반도체 집적 회로와 같은 여러 응용 분야에 사용될 수 있다.The electrolyte according to the present invention maintains its amorphous form by low temperature process, whereby high charge carrier concentration, high vacancy or interstitial site concentration, low ion transfer activation energy. Has high ionic conductivity. In the electrolyte of the present invention, Si, P, and N materials added to Li-BO contribute to the structural stabilization of the network, thereby improving the bonding strength, bonding properties, relative strength of the bonds, and reactivity with lithium ions to improve structural and chemical properties. It shows stable characteristics. Therefore, the electrolyte may be used for various applications such as micro sensors, medical devices, semiconductor integrated circuits as well as thin film cells.
[실시예]EXAMPLE
이하, 본 발명의 바람직한 실시예를 제시한다. 다만, 하기 실시예는 본 발명의 이해를 돕기 위하여 제시되는 것일 뿐 본 발명이 하기 실시예에 한정되는 것은 아니다.Hereinafter, a preferred embodiment of the present invention. However, the following examples are only presented to aid the understanding of the present invention, and the present invention is not limited to the following examples.
실시예 1: 고체 박막 전해질 제조Example 1 Preparation of Solid Thin Film Electrolyte
a) 타겟의 제작a) creation of the target
Li2B4O7 분말(Aldrich, 순도: 98 % 이상) 7.36g, Li2SiO3 (Aldrich, 순도: 99% 이상) 2.17g 및 Li3PO4(Aldrich, 순도: 99% 이상) 20.17g을 습식 볼 밀링을 행한 후, 오븐에서 6 시간 이상 건조를 하였다. 얻어진 분말을 4℃/min의 승온 속도로 600℃ 까지 승온 시킨 후, 90 분간 예비 열처리를 하였다. 다시 유발에서 분쇄하여 2 인치 디스크 형태로 제작하였다. 압착된 디스크를 4℃/min의 승온 속도로 800 ℃로 승온 시킨 후, 상기 온도에서 3 시간 동안 열처리하여, Li-B-Si-P-O의 성분을 갖는 타겟을 제작하였다.7.36 g of Li 2 B 4 O 7 powder (Aldrich, purity: 98% or more), 2.17 g of Li 2 SiO 3 (Aldrich, purity: 99% or more) and 20.17 g of Li 3 PO 4 (Aldrich, purity: 99% or more) After wet ball milling, it dried in the oven for 6 hours or more. The obtained powder was heated up to 600 ° C at a temperature increase rate of 4 ° C / min, and then preheated for 90 minutes. It was ground again in a mortar and produced in the form of a 2-inch disk. The compressed disk was heated to 800 ° C. at a temperature increase rate of 4 ° C./min, and then heat-treated at the temperature for 3 hours to prepare a target having a component of Li-B-Si-PO.
b) 고체 박막 전해질의 제작b) Fabrication of solid thin film electrolyte
챔버 내 진공을 2 ×10-6 torr 이하까지 배기하고, 챔버에 N2 가스 (순도: 99.9999 %)를 25sccm으로 흘려주면서 배기 밸브를 조절하여 챔버 내의 진공이 10mtorr가 유지되도록 하였다. 그 후, 스퍼터링 파워를 75W가 되도록 하고, 스퍼터링을 수행하는 동안 기판을 회전시키면서, RF 스퍼터링을 8∼10 시간 동안 실시하여, 약 1 ㎛ 정도의 두께를 갖는 Li-B-Si-P-O-N을 함유하는 고체 박막 전해질을 제작하였다.The vacuum in the chamber was evacuated to 2 × 10 −6 torr or less, and the exhaust valve was adjusted while flowing N 2 gas (purity: 99.9999%) at 25 sccm to maintain 10 mtorr of vacuum in the chamber. Thereafter, the sputtering power is set to 75 W, the RF sputtering is performed for 8 to 10 hours while the substrate is rotated during the sputtering, and contains Li-B-Si-PON having a thickness of about 1 μm. A solid thin film electrolyte was prepared.
실시예 2: 고체 박막 전해질의 제조Example 2: Preparation of Solid Thin Film Electrolyte
상기 증착된 실시예 1의 고체 박막 전해질 내부의 구조적 안정화를 위해 RF 플라즈마 처리를 하였다. 증착된 박막 전해질을 타겟 위치에 고정시키고, 2 ×10-6 torr 까지 배기하였다. 플라즈마 처리에 사용된 가스는 Ar, N, O 중에서 하나 이상을 선택하여 사용하였으며, 각각의 가스를 일정한 비율로 혼합하여 챔버 내로 흘려 보냈다. 형성된 플라즈마에 의한 박막 전해질이 구조적으로 안정화될 수 있을 정도의 입사되는 입자의 약한 운동 에너지를 전달하기 위해 RF 전력을 1 W 정도로 인가하였다. 플라즈마 처리 시간은 약 2 분 내지 3분 정도로 하였다.RF plasma treatment was performed to structurally stabilize the deposited thin film electrolyte of Example 1. The deposited thin film electrolyte was fixed at the target position and evacuated to 2 x 10 -6 torr. The gas used for the plasma treatment was selected by using one or more of Ar, N, O, and the respective gases were mixed in a constant ratio and flowed into the chamber. RF power was applied to about 1 W in order to deliver the weak kinetic energy of the incident particles to the extent that the thin film electrolyte by the formed plasma could be structurally stabilized. The plasma treatment time was about 2 to 3 minutes.
상기 실시예는 Li-B-Si-P-O-N을 포함하는 고체 전해질에 대해서 기술되어 있으나, 상기 실시예를 다양한 네트워크 형성제 및 개질제에 적용하는 것은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 자명할 것이다.Although the above embodiment has been described with respect to a solid electrolyte including Li-B-Si-PON, the application of the above embodiment to various network formers and modifiers will be appreciated by those skilled in the art. Will be self explanatory.
본 발명의 리튬 이온 전도 전해질은 기존의 전해질에 비해 안정성이 우수하고, 전극과의 반응성이 낮으며, 계속적인 충방전에도 안정하여 오랜 싸이클 수명을 갖는다. 이러한 물성으로 인하여 차세대 전지로 각광 받고 있는 박막 전지 및 초소형 센서 등과 같은 여러 응용 분야에 사용될 수 있다.The lithium ion conducting electrolyte of the present invention has excellent stability, low reactivity with the electrode, and is stable even with continuous charging and discharging, and has a long cycle life, as compared with a conventional electrolyte. Due to these physical properties, it can be used in various applications such as thin film cells and micro sensors, which are spotlighted as next generation batteries.
또한, 본 발명의 전해질은 국내 유수 기업에서 축적된 박막 증착 기술을 응용하여 제조될 수 있음으로, 기존의 전해질이 해외로부터 제작 공정, 설비 및 기술을 이전해 옴으로 발생하는 외화 유출 및 기술의 종속화로부터 벗어날 수 있기 때문에 국익의 증대와 국내 산업의 발전 및 관련 기술의 발전과 세계적으로 개발되고 있는 박막 전지 등의 응용 분야 기술을 선점할 수 있다는 장점을 가지고 있다.In addition, since the electrolyte of the present invention can be manufactured by applying the thin film deposition technology accumulated in the domestic leading companies, the foreign currency outflow and subordinated technology caused by the existing electrolyte transfer the manufacturing process, equipment and technology from abroad Since it can escape from the market, it has the advantage of increasing the national interests, the development of the domestic industry, the development of related technologies, and the preoccupation of application technologies such as thin film batteries that are being developed around the world.
본 발명의 단순한 변형 또는 변경은 모두 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다. All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
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