KR20190038776A - All-solid secondary battery including sulfur composite electrode with reduced carbon content - Google Patents
All-solid secondary battery including sulfur composite electrode with reduced carbon content Download PDFInfo
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- KR20190038776A KR20190038776A KR1020190037726A KR20190037726A KR20190038776A KR 20190038776 A KR20190038776 A KR 20190038776A KR 1020190037726 A KR1020190037726 A KR 1020190037726A KR 20190037726 A KR20190037726 A KR 20190037726A KR 20190038776 A KR20190038776 A KR 20190038776A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 36
- 239000011593 sulfur Substances 0.000 title claims abstract description 36
- 239000007787 solid Substances 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title claims description 22
- 239000002131 composite material Substances 0.000 title description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 21
- 239000010439 graphite Substances 0.000 claims abstract description 21
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007784 solid electrolyte Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000005087 graphitization Methods 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- 229910000676 Si alloy Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000006182 cathode active material Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003701 mechanical milling Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910018091 Li 2 S Inorganic materials 0.000 description 2
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 1
- NULBAXYJOJYNBB-UHFFFAOYSA-N S=S.[Li] Chemical compound S=S.[Li] NULBAXYJOJYNBB-UHFFFAOYSA-N 0.000 description 1
- OSJUEQHMUZRYRU-UHFFFAOYSA-N [S-2].[Li+].S.[Li+] Chemical compound [S-2].[Li+].S.[Li+] OSJUEQHMUZRYRU-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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Abstract
본 발명은 황(sulfur)을 함유하는 양극 및 양극 집전체 사이에 개재(介在)된 흑연 시트(graphite sheet)를 포함하는 리튬-황 전고체전지에 관한 것으로서, 본 발명에 따른 리튬-황 전고체전지는 집전체층과 양극층 간의 원활한 전자이동을 가능케하는 흑연 시트를 전극 및 양극 집전체 사이에 삽입시킴으로써, 이차전지 전체 부피를 현저히 감소시킴과 동시에 부피당 용량을 크게 증가시킬 수 있다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium-sulfur solid battery including a graphite sheet interposed between a positive electrode containing a sulfur and a positive electrode current collector, By inserting a graphite sheet between the electrode and the positive electrode current collector for enabling smooth electron transfer between the collector layer and the anode layer, the total volume of the secondary battery can be remarkably reduced and the capacity per unit volume can be greatly increased.
Description
본 발명은 전고체전지에 대한 것으로서, 보다 상세하게는, 카본 함량이 감소된 황 복합 전극을 포함하는 리튬-황 전고체전지에 대한 것이다.The present invention relates to a pre-solid battery, and more particularly to a lithium-sulfur pre-solid battery comprising a sulfur composite electrode with reduced carbon content.
이차전지의 양극재는 전지 구성요소 중 약 20%의 단가를 차지하는데, 황(sulfur)은 자원이 풍부하고 이론 용량이 커 이차전지의 양극재로 사용할 경우 대용량 전지를 낮은 가격으로 제조할 수 있다. 이러한 제조단가와 에너지 밀도에서의 장점 때문에 최근 리튬-황 전지에 대한 연구가 현재 진행 중에 있다.The cathode material of the secondary battery accounts for about 20% of the battery component, and sulfur is rich in resources and the theoretical capacity is large, so that a large capacity battery can be manufactured at a low price when used as a cathode material of a secondary battery. Due to these advantages in manufacturing cost and energy density, research on lithium-sulfur batteries is currently underway.
하지만 유기성 액체 전해질을 사용한 리튬-황 전지는 충/방전 시 양극에서 형성된 lithium polysulfide가 전해질에 용해되어 그 결과로 전지의 활물질이 점차 감소하여 전지의 수명이 짧아진다. 또한, 액체 전해질 사용 시 음극의 경우 리튬 금속의 표면에서 리튬 수지상(Li dendrites)의 형성은 분리막을 손상시켜 전지 내부의 단락을 유발할 수 있다.However, in the lithium-sulfur battery using the organic liquid electrolyte, the lithium polysulfide formed in the anode during charging / discharging is dissolved in the electrolyte, and as a result, the active material of the battery is gradually reduced, shortening the life of the battery. Also, when a liquid electrolyte is used, the formation of lithium dendrites on the surface of the lithium metal in the case of the negative electrode may damage the separator and cause a short circuit inside the battery.
이러한 황 용출 문제와 리튬 수지상 형성을 근본적으로 해결하기 위하여 폴리머나 세라믹 재료를 적용한 전고체 리튬-황 전지 시스템에 대한 연구가 최근 활발하게 진행되고 있다. 고체전해질의 적용으로 리튬 금속의 수지상 성장을 억제 할 수 있을 뿐 아니라 polysulfide 황 용출 문제도 함께 해결할 수 있을 것이라 기대된다.In order to fundamentally solve the sulfur leaching problem and the formation of a lithium resin phase, researches have been actively conducted on a pre-solid lithium-sulfur battery system using a polymer or a ceramic material. It is expected that the application of the solid electrolyte will not only suppress the dendritic growth of the lithium metal but also solve the polysulfide sulfur leaching problem.
하지만 고체 전해질을 사용하는 전고체전지는 전해질과 접촉하는 전극의 면적이 액체전해질을 사용할 경우에 비하여 매우 제한적이다. 이를 해결하기 위하여 황 양극 제조 시 고체전해질을 포함하여 제조해야 하며 또한 황은 전자전도성이 매우 낮은 절연성 물질이므로 추가적인 도전재로서 카본(carbon)을 첨가하여 전자 전도 통로를 충분히 제공해야한다.However, the area of the electrode contacting the electrolyte is very limited as compared with the case where the liquid electrolyte is used. In order to solve this problem, it is necessary to prepare solid electrolytes in the production of sulfur anodes. In addition, since sulfur is an insulating material having a low electron conductivity, it is necessary to provide carbon conduction by adding carbon as an additional conductive material.
하지만, 카본은 밀도가 낮아 황의 도전재로 사용할 경우 전체 전지의 부피를 증가시키는 요인이 된다.However, since carbon has low density, it becomes a factor to increase the volume of the whole battery when it is used as a conductive material of sulfur.
본 발명이 해결하고자 하는 기술적 과제는, 황 복합 전극에 포함되는 카본 함량을 줄여 전지 전체의 부피를 줄임과 동시에, 도전재인 카본 함량 감소에 따른 전지 성능 저하 또한 방지할 수 있는 리튬-황 전고체전지를 제공하는 것이다.SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems occurring in the prior art, and it is an object of the present invention to provide a lithium-sulfur composite battery capable of reducing the amount of carbon contained in a sulfur composite electrode to reduce the volume of the entire battery, .
상기 기술적 과제를 달성하기 위해, 본 발명은 황(sulfur)을 함유하는 양극 및 양극 집전체 사이에 개재(介在)된 흑연 시트(graphite sheet)를 포함하는 리튬-황 전고체전지를 제안한다.In order to accomplish the above object, the present invention proposes a lithium-sulfur pre-solid battery including a graphite sheet interposed between a cathode containing sulfur and a cathode current collector.
여기서, 상기 흑연 시트는, 고분자 시트를 열분해에 의해 흑연화(graphitization)시켜 형성된 것을 특징으로 한다.Here, the graphite sheet is formed by graphitization of a polymer sheet by thermal decomposition.
또한, 상기 흑연 시트는 열분해 흑연 시트(pyrolytic graphite sheet, PGS)인 것을 특징으로 한다.Further, the graphite sheet is a pyrolytic graphite sheet (PGS).
또한, 상기 양극은 황, 고체전해질 및 카본(carbon)을 포함하는 것을 특징으로 한다.Further, the anode is characterized by containing sulfur, a solid electrolyte and carbon.
또한, 상기 양극은, 황 100 중량부당 카본 50 중량부 이하를 포함하는 것을 특징으로 하며, 또한, 상기 양극은 황 100 중량부당 고체전해질 150 중량부 내지 250 중량부를 포함할 수 있다.In addition, the anode includes 50 parts by weight or less of carbon per 100 parts by weight of sulfur, and the anode may include 150 parts by weight to 250 parts by weight of solid electrolyte per 100 parts by weight of sulfur.
또한, 상기 고체전해질은 황화물계 전해질인 것이 바람직하며, 일례로, Li2S-P2S5일 수 있다.In addition, the solid electrolyte is preferably a sulfide-based electrolyte, and may be, for example, Li 2 SP 2 S 5 .
그리고, 본 발명은 발명의 다른 측면에서, (a) 황화물계 고체전해질 분말을 가압하여 고체전해질층을 형성시키는 단계; (b) 황, 고체전해질 및 카본을 포함하는 분말을 상기 고체전해질층의 일면에 구비시킨 후 가압하여 양극층을 형성시키는 단계; (c) 흑연 시트(graphite sheet)를 상기 양극층 상에 적층시키는 단계; 및 (d) 음극 분말을 상기 고체전해질층의 타면에 구비시킨 후, 가압하여 음극층을 형성시키는 단계를 포함하는 리튬-황 전고체전지의 제조방법을 제안한다.According to another aspect of the present invention, there is provided a method of manufacturing a solid electrolyte, comprising the steps of: (a) forming a solid electrolyte layer by pressing a sulfide-based solid electrolyte powder; (b) providing a powder containing sulfur, a solid electrolyte and carbon on one side of the solid electrolyte layer and then pressing to form a positive electrode layer; (c) depositing a graphite sheet on the anode layer; And (d) providing a negative electrode powder on the other surface of the solid electrolyte layer, followed by pressing to form a negative electrode layer.
이때, 상기 고체전해질 분말은 입자 크기를 미세화하여 고체와 고체 간의 계면 특성을 향상시키도록 구성하는 것이 바람직하며, 예를 들어, 황화리튬(Li2S)과 황화인(P2S5)의 혼합 분말을 메커니컬 밀링(mechanical milling) 방법으로 분쇄하고 기계적으로 서로 결합시켜 양극에 적합한 황화리튬-황화인(Li2S-P2S5)인 미세 고체전해질 분말을 제조할 수 있다.At this time, it is preferable that the solid electrolyte powder is configured so as to improve the interface characteristics between the solid and the solid by making the particle size finer. For example, a mixture of lithium sulfide (Li 2 S) and phosphorus sulfide (P 2 S 5 ) The powders are pulverized by a mechanical milling method and mechanically bonded to each other to prepare a fine solid electrolyte powder which is lithium sulfide-lithium sulfide (Li 2 SP 2 S 5 ) suitable for the positive electrode.
상기한 메커니컬 밀링(mechanical milling) 방법은, 복수 개의 지르코니아 볼을 이용한 유성 볼 밀링(planetary ball milling) 방법을 대표적인 예로 들 수 있으나, 이에 제한받는 것은 아니다.The mechanical milling method described above is a typical example of a planetary ball milling method using a plurality of zirconia balls, but the present invention is not limited thereto.
참고로, 상기 황화리튬(Li2S)과 황화인(P2S5)은 원료단계에서는 이온이 움직이는 전도성이 매우 적어 고체전해질로서는 사용할 수 없으나, 메커니컬 밀링 방법으로 처리한 후에는 양극에 적합한 황화리튬-황화인(Li2S-P2S5)의 고체전해질 분말로 제조되어 이온 전도성이 엄청나게 향상되어 전지 재료로서의 이용이 가능한 수준에 이른다.For reference, lithium sulfide (Li 2 S) and phosphorus sulfide (P 2 S 5 ) can not be used as solid electrolytes due to the low conductivity of ions moving in the raw material stage. However, after the treatment with the mechanical milling method, (Li 2 SP 2 S 5 ) lithium-sulfur sulfide (Li 2 SP 2 S 5 ), and the ionic conductivity is remarkably improved, reaching a level that can be used as a battery material.
한편, 상기 본 발명에 따른 리튬-황 전고체전지의 제조방법에 있어서, 상기 흑연 시트는 고분자 시트를 열 분해에 의해 흑연화(graphitization)시켜 형성된 것을 특징으로 한다.Meanwhile, in the method for manufacturing a lithium-sulfur pre-solid battery according to the present invention, the graphite sheet is formed by graphitization of a polymer sheet by thermal decomposition.
또한, 본 발명에 따른 리튬-황 전고체전지의 제조방법에 있어서, 상기 흑연 시트는 열분해 흑연 시트(pyrolytic graphite sheet, PGS)인 것을 특징으로 한다.Further, in the method for manufacturing a lithium-sulfur pre-solid battery according to the present invention, the graphite sheet is a pyrolytic graphite sheet (PGS).
또한, 본 발명에 따른 리튬-황 전고체전지의 제조방법에 있어서, 상기 음극층은 Li-Si 합금을 포함하는 것을 특징으로 한다.Further, in the method for manufacturing a lithium-sulfur pre-solid battery according to the present invention, the cathode layer includes a Li-Si alloy.
본 발명에 따른 리튬-황 전고체전지는 집전체층과 양극층 간의 원활한 전자이동을 가능케 하는 흑연 시트를 전극 및 양극 집전체 사이에 삽입시킴으로써, 이차전지 전체 부피를 현저히 감소시킴과 동시에 부피당 용량을 크게 증가시킬 수 있다.The lithium-sulfur high-voltage battery according to the present invention can reduce the volume of the secondary battery significantly by inserting a graphite sheet between the electrode and the positive electrode current collector to enable smooth electron transfer between the current collector layer and the positive electrode layer, .
도 1은 본원 실시예에 따른 리튬-황 전고체전지 제작 공정을 모식적으로 나타낸 도면이다.
도 2(a)는 비교예에 따른 종래의 리튬-황 전고체전지의 단면 구조에 대한 모식도이고, 도 2(b)는 본원 실시예에 따른 PGS를 적용한 리튬-황 전고체전지의 단면 구조에 대한 모식도이다.
도 3은 비교예에 따른 전고체전지와 본원 실시예에 따른 전고체전지 각각의 단위 무게당 충·방전 용량 그래프이다.
도 4는 비교예에 따른 전고체전지와 본원 실시예에 따른 전고체전지 각각의 단위 부피당 충·방전 용량 그래프이다.1 is a diagram schematically showing a process of manufacturing a lithium-sulfur pre-solid battery according to the present embodiment.
FIG. 2 (a) is a schematic view of a cross-sectional structure of a conventional lithium-sulfur solid battery according to a comparative example, and FIG. 2 (b) It is a schematic diagram.
FIG. 3 is a graph of charge / discharge capacity per unit weight of the pre-solid battery according to the comparative example and the pre-solid battery according to the present embodiment.
FIG. 4 is a graph of charge / discharge capacity per unit volume of the pre-solid battery according to the comparative example and the pre-solid battery according to the present embodiment.
본 발명을 설명함에 있어서 관련된 공지 기능 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략할 것이다.In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
본 발명의 개념에 따른 실시예는 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있으므로 특정 실시예들을 도면에 예시하고 본 명세서 또는 출원에 상세하게 설명하고자 한다. 그러나 이는 본 발명의 개념에 따른 실시 예를 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.Embodiments in accordance with the concepts of the present invention can make various changes and have various forms, so that specific embodiments are illustrated in the drawings and described in detail in this specification or application. It should be understood, however, that the embodiments according to the concepts of the present invention are not intended to be limited to any particular mode of disclosure, but rather all variations, equivalents, and alternatives falling within the spirit and scope of the present invention.
본 명세서에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 명세서에서, "포함하다" 또는 "가지다" 등의 용어는 설시된 특징, 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises ", or" having ", or the like, specify that there is a stated feature, number, step, operation, , Steps, operations, components, parts, or combinations thereof, as a matter of principle.
이하, 본 발명을 실시예를 들어 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in detail with reference to examples.
황은 상온에서 약 5×10-30 S/m의 매우 낮은 전자 전도도를 띄며 이를 전고체전지의 양극재로 사용할 경우 전자이동 통로를 생성하기 위하여 별도의 도전재를 첨가하여야한다. 카본의 밀도는 약 2.2g/cm3으로 전지의 부피당 용량을 저하시키는 요인이 된다.Sulfur has a very low electronic conductivity of about 5 × 10 -30 S / m at room temperature. When it is used as a cathode material of all solid-state cells, a separate conductive material should be added to generate an electron transfer path. The density of carbon is about 2.2 g / cm < 3 > which causes the capacity per unit volume of the battery to be lowered.
본 발명에서는 황 복합전극의 카본 함량을 줄이고 양극과 집전체 사이에 PGS (Pyrolytic Graphite Sheet)를 삽입하는 방법으로 전지의 용량과 가역성에 영향을 미치지 않으면서 전극의 부피를 감소시킬 수 있는 방안을 제시하고자 한다.In the present invention, a method of reducing the carbon content of the sulfur composite electrode and inserting PGS (Pyrolytic Graphite Sheet) between the anode and the current collector reduces the volume of the electrode without affecting the capacity and reversibility of the battery I want to.
전형적인 황 복합전극(비교예)의 고체전해질과 황, 카본의 비율은 4: 2: 2이며, PGS 삽입 구조(실시예)의 경우 황 복합전극 카본의 양을 반으로 줄여 4: 2: 1 비율로 전극을 제조하여 테스트하였으며, 이하 상세히 설명한다.The ratio of solid electrolyte to sulfur and carbon in a typical sulfur composite electrode (comparative example) is 4: 2: 2. In case of PGS insertion structure (example), the amount of sulfur composite electrode carbon is reduced to half, Were prepared and tested and are described in detail below.
1) 양극재 (sulfur+carbon+solid electrolyte) 제조1) Manufacture of cathode (sulfur + carbon + solid electrolyte)
① Ball milling으로 제조된 황 복합양극(비교예에 따른 전고체전지 제조용 양극)(1) A sulfur composite anode manufactured by ball milling (a cathode for manufacturing all solid-state cells according to a comparative example)
구성물질의 부피 비를 고려하여 solid electrolyte, sulfur, carbon을 2 : 1 : 1 (wt%) 비율로 혼합한다. 물질의 고른 분산을 위하여 planetary ball milling 방법을 채택하였다. Milling pot에 분말형태의 각 구성요소와 5φ의 zirconia ball을 BPR (ball to powder weight ratio) 50:1 (wt%)로 넣고 milling pot 내부 Ar분위기를 유지하기 위하여 glove box내에서 sealing한다. Sealing된 milling pot를 370rpm으로 planetary ball milling하면 균일한 분포를 가지는 composite cathode가 제조된다. Solid electrolyte, sulfur, and carbon are mixed at a ratio of 2: 1: 1 (wt%) considering the volume ratio of constituent materials. A planetary ball milling method was adopted for uniform dispersion of materials. Put each component of powder form and zirconia ball of 5φ into a milling pot with a ball to powder weight ratio (BPR) of 50: 1 (wt%) and seal in a glove box to maintain the Ar atmosphere inside the milling pot. A planar ball milling of the sealed milling pot at 370 rpm produces a uniformly distributed composite cathode.
② 카본 함량을 감소시킨 황 복합양극(본원 실시예에 따른 전고체전지 제조용 양극)(2) A sulfur composite anode having reduced carbon content (anode for producing all-solid-state cells according to the present embodiment)
Solid electrolyte, sulfur, carbon을 4 : 2 : 1 (wt%) 비율로 milling pot에 넣고 ①과 동일한 조건에서 제조한다. Solid electrolyte, sulfur, and carbon are put into a milling pot at a ratio of 4: 2: 1 (wt%), and are manufactured under the same conditions as ①.
2) 황화물계 고체전해질(Li2S-P2S5) 제조 - 본 발명의 성능 평가를 위한 전해질 제조2) Preparation of sulfide-based solid electrolyte (Li2S-P2S5) - Preparation of electrolyte for performance evaluation of the present invention
Bulk type 의 전고체전지 제조가 용이하고, 황 전극과의 부 반응을 최소화 할 수 있는 황화물계 고체전해질을 제조한다. 황화물계 고체전해질 중 상온에서 비교적 높은 이온전도도를 가지는 Li2S-P2S5를 선택 한다. Milling pot에 7:3의 mol%의 70Li2S-30P2S5와 10φ zirconia ball 10개를 넣어 BPR 100:1 (wt%). 370rpm으로 planetary ball milling 을 실시한다. 양극재와 마찬가지로 Glove box내에서 진행한다. A sulfide-based solid electrolyte capable of easily producing all-solid-state batteries of a bulk type and minimizing adverse reaction with a sulfur electrode is prepared. Among the sulfide-based solid electrolytes, Li 2 SP 2 S 5 having a relatively high ionic conductivity at room temperature is selected. In a milling pot, add 70Li 2 S-30P 2 S 5 and 10φ zirconia balls in a molar ratio of 7: 3 to BPR 100: 1 (wt%). Perform planetary ball milling at 370 rpm. It proceeds in the glove box as well as the cathode material.
3) 음극재 (Li3) Anode material (Li 4.44.4 Si) 제조 - 본 발명의 성능 평가를 위한 음극 제조Si) - Preparation of negative electrode for performance evaluation of the present invention
Li 합금화 원소 중 높은 부피당 용량을 가지는 LI-Si alloy를 제조하여 전고체전지의 음극재로 적용한다. 양극재, 고체전해질과 마찬가지로 glove box내에서 제조한다. Granular 형태의 Li 0.213g과 Si 분말 0.196g을 milling pot에 넣고 BPR 110:1 (wt%) 조건으로 5φ, 10φ zirconia ball을 함께 넣어준 후 370rpm으로 planetary ball milling 을 실시한다. LI-Si alloy having high capacity per volume of Li alloying elements is prepared and applied to the anode material of all solid-state batteries. Like the cathode material and the solid electrolyte, it is manufactured in a glove box. 0.213g of granular Li and 0.196g of Si powder were put into a milling pot and 5φ and 10φ zirconia balls were added under the condition of BPR 110: 1 (wt%), followed by planetary ball milling at 370 rpm.
4) 전고체 리튬-황 전지 full cell 제조4) Manufacture full solid lithium-sulfur battery full cell
① 비교예에 따른 전고체전지의 제조(도 2(a) 참조)(1) Production of all solid batteries according to Comparative Example (see Fig. 2 (a)) [
- 지름 14φ로 제작된 알루미나 몰드에 전해질 0.1g을 넣고 oil pressure machine으로 25MPa의 압력을 가해 disc pellet 형태로 성형한다.- Add 0.1 g of electrolyte to an alumina mold with a diameter of 14φ and apply pressure of 25 MPa using an oil pressure machine to form a disc pellet.
- 고체전해질/ 황/ 카본을 2 : 1 : 1 (wt%)비율로 혼합하여 제조한 복합전극을 양극으로 사용한다. (Solid electrolyte / sulfur / carbon) at a ratio of 2: 1: 1 (wt%) is used as a positive electrode.
- (양극 활물질 S: 0.04g) 양극을 몰드 한쪽에 넣은 후 압력을 가하여 양극층을 만든다.- (Cathode active material S: 0.04 g) The positive electrode is put on one side of the mold and pressure is applied to make the positive electrode layer.
- 양극 활물질 질량에 맞추어 Li-Si 음극 활물질 0.04g을 몰드 반대편에 넣고 압력을 가해 음극층을 만든다.- According to the mass of the cathode active material, 0.04 g of Li-Si negative electrode active material is put on the opposite side of the mold and pressure is applied to make the cathode layer.
② 실시예에 따른 전고체전지의 제조(도 2(b) 참조)(2) Production of all solid batteries according to the embodiment (see Fig. 2 (b)
- 지름 14φ로 제작된 알루미나 몰드에 전해질 0.1g을 넣고 oil pressure machine으로 25MPa의 압력을 가해 disc pellet 형태로 성형한다.- Add 0.1 g of electrolyte to an alumina mold with a diameter of 14φ and apply pressure of 25 MPa using an oil pressure machine to form a disc pellet.
- 고체전해질/ 황/ 카본을 4 : 2 : 1 (wt%)비율로 혼합하여 제조한 복합 전극을 양극으로 사용한다.(양극 활물질 S: 0.04g) 양극을 몰드 한쪽에 넣은 후 압력을 가하여 양극 층을 만든다. (Cathode active material S: 0.04 g). The positive electrode was placed on one side of the mold and the pressure was applied to the positive electrode (positive electrode active material S: 0.04 g). The positive electrode was prepared by mixing the solid electrolyte / sulfur / carbon at a ratio of 4: Create a layer.
- 황 복합 양극 위에 PGS를 적층하여 경사구조의 양극을 만든다. 참고로, 상기PGS (Pyrolytic Graphite Sheet): PGS의 전기전도도는 1×104S/cm이며 두께는 약 0.017mm로 집전체와 양극사이에 삽입할 경우 전지의 부피에 큰 변화를 미치지 않으며 전자전도가 원활하게 이루어지게 한다.- The positive electrode of the gradient structure is made by stacking PGS on the sulfur composite anode. For reference, the electric conductivity of the PGS (Pyrolytic Graphite Sheet): PGS is 1 x 10 4 S / cm and the thickness is about 0.017 mm. When inserted between the current collector and the anode, the volume of the battery is not significantly changed, .
- 양극 활물질 질량에 맞추어 Li-Si 음극 활물질 0.04g을 몰드 반대편에 넣고 압력을 가해 음극층을 만든다.- According to the mass of the cathode active material, 0.04 g of Li-Si negative electrode active material is put on the opposite side of the mold and pressure is applied to make the cathode layer.
5) 실시예 및 비교예에서 제조된 전고체 리튬-황 전지에 대한 충5) For all solid lithium-sulfur batteries prepared in Examples and Comparative Examples ·· 방전 실험Discharge experiment
상기에 따라 제조된 실시예 및 비교예 각각에 따른 전고체전지에 대해 200㎂ 정전류 하에서 충·방전 실험을 진행하였으며, 충·방전 실험 이후 몰드에서 분리하여 전지의 두께를 측정하였다.Charging and discharging tests were carried out at a constant current of 200 전 for all the solid-state batteries prepared according to the above-described Examples and Comparative Examples. The thickness of the battery was measured by separating from the mold after the charging and discharging tests.
황 활물질 무게 당 용량을 비교할 경우 본원 실시예에 따른 전고체전지의 용량이 비교예에 따른 전고체전지의 1cycle 이후 용량과 동등한 수준임을 볼 수 있다(도 3 참조). When the capacity per weight of sulfur active material is compared, it can be seen that the capacity of the all solid battery according to the present embodiment is equivalent to the capacity after 1 cycle of the all solid battery according to the comparative example (see FIG. 3).
즉, PGS 도입으로 무게 당 용량 감소와 같은 부 효과는 미미한 것으로 판단된다. 본원 실시예에 따른 전고체전지의 황 복합 양극의 도전재 양을 감소시켰지만 PGS를 통해 전자전도가 원활히 이루어져 황 활물질 무게 당 용량은 감소되지 않았다는 것을 보여준다.In other words, the adverse effects such as the decrease in the weight-bearing capacity due to introduction of PGS are considered to be insignificant. The amount of the conductive material in the sulfur composite anode of the pre-solid battery according to the present embodiment was reduced, but the electron conduction was smoothly conducted through the PGS, so that the capacity per weight of the sulfur active material was not reduced.
본원 실시예에 따른 전고체전지의 양극 부피는 비교예에 따른 전고체전지에 비해 1/1.5 수준이기 때문에 본원 실시예에 따른 전고체전지의 단위 부피 당 용량이 비교예에 따른 전고체전지에 비하여 약 1.6배 이상 증가한 것을 볼 수 있다(도 4 참조).Since the anode volume of the all-solid-state cell according to the present embodiment is about 1 / 1.5 of the total solid-state cell according to the comparative example, the capacity per unit volume of the all solid- It is seen that it increased about 1.6 times or more (see FIG. 4).
상기 결과로부터, 본 발명에 의하면 양극의 도전재를 감소시킴으로써 전지의 부피를 감소시켰을 뿐만 아니라 PGS를 도입을 통하여 도전재 감소로 인한 부 효과는 방지하였음을 알 수 있다.From the above results, it can be seen that the present invention not only reduced the volume of the battery by reducing the conductive material of the anode but also prevented the negative effect due to the reduction of the conductive material through introduction of PGS.
Claims (10)
상기 흑연 시트는, 고분자 시트를 열분해에 의해 흑연화(graphitization)시켜 형성된 것을 특징으로 하는 리튬-황 전고체전지.The method according to claim 1,
Wherein the graphite sheet is formed by graphitization of a polymer sheet by thermal decomposition.
상기 흑연 시트는 열분해 흑연 시트(pyrolytic graphite sheet, PGS)인 것을 특징으로 하는 리튬-황 전고체전지.3. The method of claim 2,
Wherein the graphite sheet is a pyrolytic graphite sheet (PGS).
상기 양극은 황, 고체전해질 및 카본(carbon)을 포함하는 것을 특징으로 하는 리튬-황 전고체전지.The method according to claim 1,
Wherein the anode comprises sulfur, a solid electrolyte and carbon.
상기 양극은, 황 100 중량부당 카본 50 중량부 이하를 포함하는 것을 특징으로 하는 리튬-황 전고체전지.5. The method of claim 4,
Characterized in that the anode comprises not more than 50 parts by weight of carbon per 100 parts by weight of sulfur.
상기 고체전해질은 Li2S-P2S5인 것을 특징으로 하는 리튬-황 전고체전지.5. The method of claim 4,
Wherein the solid electrolyte is Li 2 SP 2 S 5 .
(b) 황, 고체전해질 및 카본을 포함하는 분말을 상기 고체전해질층의 일면에 구비시킨 후 가압하여 양극층을 형성시키는 단계;
(c) 흑연 시트를 상기 양극층 상에 적층시키는 단계; 및
(d) 음극 분말을 상기 고체전해질층의 타면에 구비시킨 후, 가압하여 음극층을 형성시키는 단계를 포함하는 리튬-황 전고체전지의 제조방법.(a) pressing the sulfide-based solid electrolyte powder to form a solid electrolyte layer;
(b) providing a powder containing sulfur, a solid electrolyte and carbon on one side of the solid electrolyte layer and then pressing to form a positive electrode layer;
(c) depositing a graphite sheet on the anode layer; And
(d) providing a negative electrode powder on the other surface of the solid electrolyte layer, and then pressing to form a negative electrode layer.
상기 흑연 시트는, 고분자 시트를 열 분해에 의해 흑연화(graphitization)시켜 형성된 것을 특징으로 하는 리튬-황 전고체전지의 제조방법.8. The method of claim 7,
Wherein the graphite sheet is formed by graphitization of a polymer sheet by thermal decomposition.
상기 흑연 시트는 열분해 흑연 시트(pyrolytic graphite sheet, PGS)인 것을 특징으로 하는 리튬-황 전고체전지의 제조방법.9. The method of claim 8,
Wherein the graphite sheet is a pyrolytic graphite sheet (PGS).
상기 음극층은 Li-Si 합금을 포함하는 것을 특징으로 하는 리튬-황 전고체전지의 제조방법.8. The method of claim 7,
Wherein the cathode layer comprises a Li-Si alloy. ≪ RTI ID = 0.0 > 11. < / RTI >
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