KR102570543B1 - 그래핀-금속 입자 복합체를 포함하는 전고체전지용 음극 및 이를 포함하는 전고체전지 - Google Patents
그래핀-금속 입자 복합체를 포함하는 전고체전지용 음극 및 이를 포함하는 전고체전지 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000002082 metal nanoparticle Substances 0.000 title 1
- 239000002923 metal particle Substances 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 claims abstract description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- -1 lithium-nickel-cobalt-aluminum Chemical compound 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910018133 Li 2 S-SiS 2 Inorganic materials 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 229910009324 Li2S-SiS2-Li3PO4 Inorganic materials 0.000 claims description 3
- 229910009320 Li2S-SiS2-LiBr Inorganic materials 0.000 claims description 3
- 229910009316 Li2S-SiS2-LiCl Inorganic materials 0.000 claims description 3
- 229910009318 Li2S-SiS2-LiI Inorganic materials 0.000 claims description 3
- 229910009328 Li2S-SiS2—Li3PO4 Inorganic materials 0.000 claims description 3
- 229910009134 Li2S—GeS2—SiS2 Inorganic materials 0.000 claims description 3
- 229910007295 Li2S—SiS2—Li3PO4 Inorganic materials 0.000 claims description 3
- 229910007291 Li2S—SiS2—LiBr Inorganic materials 0.000 claims description 3
- 229910007288 Li2S—SiS2—LiCl Inorganic materials 0.000 claims description 3
- 229910007289 Li2S—SiS2—LiI Inorganic materials 0.000 claims description 3
- 229910007306 Li2S—SiS2—P2S5LiI Inorganic materials 0.000 claims description 3
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims description 3
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 3
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910007281 Li2S—SiS2—B2S3LiI Inorganic materials 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001316 Ag alloy Inorganic materials 0.000 claims 2
- 239000006183 anode active material Substances 0.000 abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 14
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000035515 penetration Effects 0.000 abstract description 4
- 230000006866 deterioration Effects 0.000 abstract description 3
- 230000001788 irregular Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000002245 particle Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000006182 cathode active material Substances 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000007771 core particle Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- 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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- Secondary Cells (AREA)
Abstract
Description
도 1b는 광열 조사 공정을 실시한 후의 은 입자(Ag)를 보여주는 주사전자현미경(SEM) 사진이다.
도 1c는 금속 입자 없이 광화학 및 광열반응으로 제조된 다공성 그래핀 구조체(3차원 나노 다공성 그래핀)을 보여주는 주사전자현미경(SEM) 사진이다.
도 1d는 본원 실시예에서 광화학 및 광열반응으로 제조한 전고체전지 음극 활물질용 그래핀-금속 입자 복합체를 보여주는 주사전자현미경(SEM) 사진이다.
도 2는 본 발명에 따른 전고체전지 음극 활물질용 그래핀-금속 입자 복합체(Graphene-Ag electrode), 그래핀 전극(Graphene electrode) 및 금속 전극(Gold electrode) 각각에 대해 전기화학 측정물질(PAP)의 농도에 따른 전류 측정 결과를 보여주는 그래프이다.
도 3은 본 발명에 따른 전고체전지 음극 활물질용 그래핀-금속 입자 복합체(Hybrid Graphene), 그래핀(Graphene) 및 금속(Metal(Au)) 각각에 대해 같은 농도(1.0ㅧ10-3mM)의 PAP에서의 전류 값을 대비해 보여주는 그래프이다.
도 4는 본 발명에 따른 전고체전지 음극용 하이브리드 그래핀 전극을 이용해 전기화학 측정물질(PAP)의 다양한 농도를 측정한 실시간 그래프이다.
도 5는 상기 본 발명에 따른 전고체전지용 음극을 포함하는 전고체전지의 일례로서, 양극 활물질(NMC)을 포함하는 양극, 황화물계 고체 전해질층, 및 음극 집전체(SUS) 및 상기 그래핀-금속 입자 복합체로 이루어진 음극 활물질을 포함하는 음극 활물질층을 포함하는 음극을 구비한 전고체전지의 단면 모식도이다.
Claims (7)
- 그래핀-금속 입자 복합체로 이루어진 음극 활물질을 포함하되,
상기 그래핀-금속 입자 복합체는,
광화학 또는 광열반응에 의해 금속 입자와 그래핀 시트 간 상호 연결이 유기적으로 이루어진 네트워크 구조로 상호 연결되며,
여러 층의 그래핀이 적층되고 임의의 방향으로 굽혀져 있는 3차원 그래핀 복합층을 포함하는 것을 특징으로 하는
전고체전지용 음극. - 삭제
- 제1항에 있어서,
상기 금속 입자는 은(Ag), 금(Au), 백금(Pt), 팔라듐(Pd), 알루미늄(Al), 아연(Zn), 은 합금 (Ag alloy), 표면이 은(Ag)으로 코팅된 구리(Cu) 및 표면이 구리(Cu)로 코팅된 은(Ag)으로 이루어진 군으로부터 선택되는 금속으로 이루어진 인 것을 특징으로 하는
전고체전지용 음극. - 삭제
- 양극 집전체 및 양극 활물질층을 포함하는 양극;
고체 전해질층; 및
제1항 또는 제3항에 따른 음극;
을 포함하는 전고체전지. - 제5항에 있어서,
상기 양극 활물질층은,
리튬-니켈-코발트-망간계 복합 산화물(NCM), 리튬-니켈-코발트-알루미늄계 복합 산화물(NCA), 리튬-코발트계 복합 산화물(LCO) 및 리튬-니켈계 복합 산화물(LNO) 이루어진 군으로부터 선택되는 1종 이상의 양극 활물질을 포함하는 것을 특징으로 하는 전고체전지. - 제5항에 있어서,
상기 고체 전해질층은,
Li2S-P2S5-LiI, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-GeS2 및 Li2S-SiS2-Li3PO4로 이루어진 군으로부터 선택되는 1종 이상의 고체 전해질을 포함하는 것을 특징으로 하는 전고체전지.
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KR101594836B1 (ko) * | 2014-04-07 | 2016-02-26 | 전남대학교산학협력단 | 그래핀-금속나노입자복합체, 상기 복합체를 포함하는 탄소나노섬유복합체 및 상기 탄소나노입자복합체를 포함하는 이차전지 |
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