KR20200007359A - Method for preparing electrode - Google Patents
Method for preparing electrode Download PDFInfo
- Publication number
- KR20200007359A KR20200007359A KR1020180081386A KR20180081386A KR20200007359A KR 20200007359 A KR20200007359 A KR 20200007359A KR 1020180081386 A KR1020180081386 A KR 1020180081386A KR 20180081386 A KR20180081386 A KR 20180081386A KR 20200007359 A KR20200007359 A KR 20200007359A
- Authority
- KR
- South Korea
- Prior art keywords
- electrode
- conductive polymer
- coated
- manganese oxide
- lithium manganese
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 79
- 239000000178 monomer Substances 0.000 claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 11
- CJYZTOPVWURGAI-UHFFFAOYSA-N lithium;manganese;manganese(3+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[O-2].[Mn].[Mn+3] CJYZTOPVWURGAI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims description 26
- 239000007772 electrode material Substances 0.000 claims description 23
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 23
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 22
- 239000004020 conductor Substances 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 21
- 239000003990 capacitor Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- 239000011572 manganese Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- -1 contact black Chemical compound 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000767 polyaniline Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002717 carbon nanostructure Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011254 layer-forming composition Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/049—Manufacturing of an active layer by chemical means
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
Description
본 발명은 전극 제조방법에 관한 것으로, 보다 자세하게는 전도성 고분자가 코팅된 전극 제조방법에 관한 것이다.The present invention relates to a method for manufacturing an electrode, and more particularly to a method for manufacturing an electrode coated with a conductive polymer.
환경 및 에너지에 대한 관심의 고조로 인하여 리튬 이차 전지, 커패시터(capacitor) 등 에너지 저장 시스템에 대한 연구가 활발히 진행되고 있다. 특히, 고용량, 고출력 특성이 요구되는 분야에 응용이 가능한 슈퍼 커패시터 및 리튬 이차 전지가 최근에 많은 주목을 받고 있다.Due to the growing interest in the environment and energy, research on energy storage systems such as lithium secondary batteries and capacitors has been actively conducted. In particular, supercapacitors and lithium secondary batteries that can be applied to fields requiring high capacity and high output characteristics have received much attention in recent years.
커패시터는 전기를 저장하는 장치로, 전해질 안에 있는 두 전극 사이에 전압을 가해줌으로써 생기는 정전 용량을 이용하는 장치이다. 슈퍼 커패시터는 일반 커패시터 보다 높은 정전 용량을 가지는 것으로 울트라 커패시터라고도 한다.Capacitors are devices that store electricity and use the capacitance created by applying a voltage between two electrodes in an electrolyte. Supercapacitors have higher capacitance than ordinary capacitors and are also called ultracapacitors.
슈퍼 커패시터는 전극으로 사용하는 물질에 따라 전기 이중층 커패시터(electric double layer capacitor), 슈도 커패시터(pseudo capacitor) 및 하이브리드 커패시터(hybrid capacitor)로 나뉘어 진다. 상기 전기 이중층 커패시터는 전기 이중층 전하 층의 원리를 이용한 것이고, 상기 슈도 커패시터는 산화 환원 반응에 의해 정전 용량을 확대한 커패시터를 말한다. 상기 하이브리드 커패시터는 상기 전기 이중층과 슈도 커패시터의 혼합 전극으로 만들어진 것을 말한다.Supercapacitors are divided into electric double layer capacitors, pseudo capacitors, and hybrid capacitors, depending on the materials used as electrodes. The electric double layer capacitor uses the principle of the electric double layer charge layer, and the pseudo capacitor refers to a capacitor in which the capacitance is enlarged by a redox reaction. The hybrid capacitor is made of a mixed electrode of the electric double layer and the pseudo capacitor.
상기 슈퍼 커패시터는 전극 표면에 전해질 이온들이 흡착됨으로써 발생하는 전기화학적 메커니즘을 이용하여 전지를 저장한다. 따라서 높은 출력을 나타내며 수만번의 충방전을 하여도 처음의 성능을 계속 유지할 수 있다.The supercapacitor stores a battery using an electrochemical mechanism generated by adsorption of electrolyte ions on an electrode surface. Therefore, it shows high output and can maintain the initial performance even after tens of thousands of charge / discharge cycles.
상기 리튬 이차 전지 및 커패시터 등의 양극재로 사용되는 리튬망간 산화물(LiMn2O4)은 148mAh/g의 정전 용량을 가지며, Li 전극 대비 4 내지 4.2V의 높은 표준환원전위를 지니고 있어 양극재로 좋은 특성을 나타낸다. 그러나, 충전시 리튬이 탈리되면서 나타나는 불균화 반응(disproportionation,2Mn+→Mn4++Mn2+)에 의해 망간이 용해(dissolution)되는 단점이 있다. 또한, 리튬염 함유 전해액으로 LiPF6을 사용할 때 상기 전해액에 수분이 미량 함유되어 있을 경우 HF에 의한 열화(degradation)에 취약한 단점이 있다.Lithium manganese oxide (LiMn 2 O 4 ), which is used as a cathode material for lithium secondary batteries and capacitors, has a capacitance of 148 mAh / g, and has a high standard reduction potential of 4 to 4.2 V relative to Li electrodes. Good properties. However, there is a disadvantage in that manganese is dissolved by disproportionation (2Mn + → Mn 4+ + Mn 2+ ), which occurs when lithium is released during charging. In addition, when LiPF 6 is used as a lithium salt-containing electrolyte solution, when the electrolyte solution contains a small amount of water, there is a disadvantage in that it is vulnerable to degradation due to HF.
이러한 리튬망간 산화물(LiMn2O4) 입자의 전기화학적 안정성 및 출력특성을 향상시키기 위하여 전극물질 표면에 전도성 물질을 고르게 코팅하는 방법이 대두되고 있다. 전극 물질 표면에 코팅할 수 있는 소재로는 전도성이 뛰어난 금속 또는 금속산화물, 탄소 소재 및 전도성 고분자 등이 있으나, 금속 또는 금속산화물의 경우 표면을 고르게 코팅하기 어려우며 탄소 소재 코팅의 경우 비활성 분위기에서 열처리시 리튬망간 산화물(LiMn2O4)의 결정상이 무너지고 환원되어 MnO나 Mn3O4로 변하여 리튬의 충방전이 불가능하다.In order to improve the electrochemical stability and output characteristics of the lithium manganese oxide (LiMn 2 O 4 ) particles, a method of evenly coating a conductive material on the surface of the electrode material has emerged. Materials that can be coated on the surface of electrode materials include metals or metal oxides, carbon materials, and conductive polymers that are highly conductive.However, metals or metal oxides are difficult to coat evenly on surfaces, and carbon coatings can be heat treated in an inert atmosphere. The crystal phase of lithium manganese oxide (LiMn 2 O 4 ) collapses and is reduced to MnO or Mn 3 O 4 , whereby charging and discharging of lithium is impossible.
따라서, 상기의 문제를 해결할 수 있는 전극물질 표면에 전도성 물질이 코팅된 전극 제조방법이 필요한 실정이다.Therefore, there is a need for an electrode manufacturing method coated with a conductive material on the surface of the electrode material that can solve the above problems.
본 발명은 전도성 고분자가 코팅된 전극 제조방법을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a method for producing an electrode coated with a conductive polymer.
상기 목적을 달성하기 위하여,In order to achieve the above object,
본 발명은 (1)리튬망간 산화물(LiMn2O4)을 포함하는 전극을 제조하는 단계;The present invention comprises the steps of preparing an electrode comprising (1) lithium manganese oxide (LiMn 2 O 4 );
(2)전도성 고분자 단량체 및 산을 혼합하여 프로톤화된 전도성 고분자 단량체 용액을 제조하는 단계; 및(2) mixing a conductive polymer monomer and an acid to prepare a protonated conductive polymer monomer solution; And
(3)상기 전극을 상기 프로톤화된 전도성 고분자 단량체 용액에 침지(soaking)시키는 단계;를 포함하는 전도성 고분자가 코팅된 전극 제조방법을 제공한다.And (3) soaking the electrode in the protonated conductive polymer monomer solution.
본 발명의 전도성 고분자가 코팅된 전극 제조방법은 전도성 고분자 단량체를 고분자화(polymerization)하기 위한 중합 개시제 또는 산화제가 필요하지 않아 간단한 방법으로 전극을 코팅할 수 있다.In the method of manufacturing an electrode coated with the conductive polymer of the present invention, a polymerization initiator or an oxidant for polymerizing the conductive polymer monomer is not required, and thus the electrode may be coated by a simple method.
또한, 본 발명의 제조방법으로 제조된 전도성 고분자가 코팅된 전극은 전기화학적 안정성이 우수한 효과를 지니고 있다.In addition, the electrode coated with a conductive polymer prepared by the manufacturing method of the present invention has an excellent electrochemical stability.
도 1은 폴리아닐린으로 코팅된 리튬망간 산화물을 50,000배 확대한 SEM 사진이다.
도 2는 폴리아닐린으로 코팅된 리튬망간 산화물을 20,000배 확대한 SEM 사진이다.
도 3은 리튬망간 산화물을 50,000배 확대한 SEM 사진이다.
도 4는 리튬망간 산화물을 20,000배 확대한 SEM 사진이다.
도 5는 실시예 1 및 비교예 1의 전극의 정전류 충방전을 측정한 그래프이다.
도 6은 실시예 1 및 비교예 1의 전극의 출력특성 그래프이다.
도 7은 실시예 1 및 비교예 1의 전극의 충방전 안정성 그래프이다.1 is a SEM photograph of 50,000 times magnification of a lithium manganese oxide coated with polyaniline.
FIG. 2 is an SEM image of 20,000 times magnification of lithium manganese oxide coated with polyaniline.
3 is an SEM image of 50,000 times magnification of lithium manganese oxide.
4 is an SEM image of 20,000 times magnification of lithium manganese oxide.
5 is a graph measuring constant current charge / discharge of the electrodes of Example 1 and Comparative Example 1. FIG.
6 is a graph of output characteristics of the electrodes of Example 1 and Comparative Example 1. FIG.
7 is a charge and discharge stability graph of the electrode of Example 1 and Comparative Example 1.
이하, 본 발명을 보다 자세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 전도성 고분자가 코팅된 전극 제조방법에 관한 것으로,The present invention relates to a method for manufacturing an electrode coated with a conductive polymer,
(1)리튬망간 산화물(LiMn2O4)을 포함하는 전극을 제조하는 단계;(1) preparing an electrode including lithium manganese oxide (LiMn 2 O 4 );
(2)전도성 고분자 단량체 및 산을 혼합하여 프로톤화된 전도성 고분자 단량체 용액을 제조하는 단계; 및(2) mixing a conductive polymer monomer and an acid to prepare a protonated conductive polymer monomer solution; And
(3)상기 전극을 상기 프로톤화된 전도성 고분자 단량체 용액에 침지(soaking)시키는 단계;를 포함한다.(3) soaking the electrode in the protonated conductive polymer monomer solution.
상기 (1)단계는 리튬망간 산화물(LiMn2O4)을 포함하는 전극을 제조하는 단계이다.Step (1) is a step of manufacturing an electrode containing lithium manganese oxide (LiMn 2 O 4 ).
상기 리튬망간 산화물은 전극 활물질이다.The lithium manganese oxide is an electrode active material.
구체적으로 상기 (1)단계의 전극 제조는 리튬망간 산화물, 도전재 및 바인더를 포함하는 전극 활물질층 형성용 조성물을 제조한 후, 상기 전극 활물질층 형성용 조성물을 집전체 상에 도포하여 전극을 제조하는 단계이다.Specifically, in the electrode preparation of step (1), after preparing a composition for forming an electrode active material layer including a lithium manganese oxide, a conductive material, and a binder, coating the composition for forming the electrode active material layer on a current collector to prepare an electrode It's a step.
상기 리튬망간 산화물은 전극 활물질층 형성용 조성물 총 중량에 대하여 65 내지 95 중량%로 포함되며, 바람직하게는 70 내지 90 중량%로 포함된다. 상기 리튬망간 산화물이 65 중량% 미만으로 포함되면 전극 활물질층의 용량이 상대적으로 낮아져 전극의 성능이 우수하지 못하며, 95 중량%를 초과하여 포함되면 전극 내 도전재 및 바인더의 함량이 상대적으로 부족해져 전하 전달이 원활하지 못하게 되어 전극 활물질 무게 대비 성능이 감소하며, 전극이 제대로 형성되지 못하고 크랙이 발생할 수 있다.The lithium manganese oxide is included in 65 to 95% by weight, preferably 70 to 90% by weight based on the total weight of the composition for forming an electrode active material layer. When the lithium manganese oxide is included in less than 65% by weight, the capacity of the electrode active material layer is relatively low, the performance of the electrode is not excellent, and when contained in excess of 95% by weight, the content of the conductive material and the binder in the electrode is relatively insufficient to charge The transfer may not be performed smoothly, and the performance decreases with respect to the weight of the electrode active material, and electrodes may not be formed properly and cracks may occur.
상기 도전재는 리튬망간 산화물에 추가적인 도전성을 부여하기 위하여 사용되는 것이며, 전자가 전극 내에서 원활하게 이동하도록 하기 위한 역할을 하는 것이다. 또한, 상기 도전재는 전지에 화학적 변화를 유발하지 않으면서 도전성이 우수하고 넓은 표면적을 제공할 수 있는 것이면 특별한 제한이 없으나, 바람직하게는 탄소계 물질을 사용한다. The conductive material is used to impart additional conductivity to the lithium manganese oxide, and serves to smoothly move electrons in the electrode. In addition, the conductive material is not particularly limited as long as it is excellent in conductivity and can provide a large surface area without causing chemical changes in the battery, but preferably a carbon-based material is used.
상기 탄소계 물질로는 천연 흑연, 인조 흑연, 팽창 흑연, 그래핀(Graphene) 과 같은 흑연(Graphite)계, 활성탄(Active carbon)계, 채널 블랙(Channel black), 퍼니스 블랙(Furnace black), 써말 블랙(Thermal black), 컨택트 블랙(Contact black), 램프 블랙(Lamp black), 아세틸렌 블랙(Acetylene black)과 같은 카본 블랙(Carbon black)계; 탄소 섬유(Carbon fiber)계, 탄소나노튜브(Carbon nanotube:CNT), 풀러렌(Fullerene)과 같은 탄소 나노 구조체 및 이들의 조합으로 이루어진 군으로부터 선택된 1종을 사용할 수 있다.The carbonaceous material may be natural graphite, artificial graphite, expanded graphite, graphite such as graphene, activated carbon, channel black, furnace black, thermal Carbon blacks such as thermal black, contact black, lamp black, acetylene black; One kind selected from the group consisting of carbon fiber-based, carbon nanotubes (CNT), carbon nanostructures such as fullerene, and combinations thereof may be used.
상기 탄소계 물질 이외에도, 목적에 따라 금속 메쉬 등의 금속성 섬유; 구리(Cu), 은(Ag), 니켈(Ni), 알루미늄(Al) 등의 금속성 분말; 또는 폴리페닐렌 유도체 등의 유기 도전성 재료도 사용할 수 있다. 상기 도전성 재료들은 단독 또는 혼합하여 사용될 수 있다.In addition to the carbon-based material, metallic fibers such as metal meshes according to the purpose; Metallic powders such as copper (Cu), silver (Ag), nickel (Ni) and aluminum (Al); Or organic conductive materials, such as a polyphenylene derivative, can also be used. The conductive materials may be used alone or in combination.
상기 도전재는 전극 활물질층 형성용 조성물 총 중량에 대하여 2 내지 20 중량%로 포함되며, 바람직하게는 3 내지 15 중량%로 포함된다. 상기 도전재가 2 중량% 미만으로 포함되면 전극 내 도전재의 함량이 부족하여 전극 활물질에 전하 전달이 제대로 이루어지지 않으며, 20 중량%를 초과하여 포함되면 전극 활물질 대비 도전재의 함량이 상대적으로 많아 전극 활물질의 비율이 더 높은 전극에 비해 전극의 성능이 낮아질 수 있다. The conductive material is included in an amount of 2 to 20% by weight, preferably 3 to 15% by weight, based on the total weight of the composition for forming an electrode active material layer. If the conductive material is included in less than 2% by weight of the conductive material in the electrode is insufficient in the charge transfer to the electrode active material is not properly made, if contained in more than 20% by weight of the conductive material relative to the electrode active material is relatively high The performance of the electrode can be lowered compared to the electrode with higher ratio.
상기 바인더는 상기 리튬망간 산화물이 집전체에 대한 부착력을 제공하기 위하여 사용되는 것이다. 상기 바인더는 용매에 잘 용해되어야 하며, 전극 활물질인 리튬망간 산화물과 도전재와의 도전 네트워크를 잘 구성해주어야 할 뿐만 아니라 전해액의 함침성도 적당히 가져야 한다.The binder is one in which the lithium manganese oxide is used to provide adhesion to a current collector. The binder should be well dissolved in a solvent, and should not only form a conductive network of lithium manganese oxide, which is an electrode active material, and a conductive material, but also have an impregnation property of an electrolyte.
본 발명에 적용 가능한 바인더는 당해 업계에서 공지된 모든 바인더들일 수 있고, 구체적으로는, 폴리비닐리덴 플루오라이드(Polyvinylidene fluoride, PVdF) 또는 폴리테트라플루오로에틸렌(Polytetrafluoroethylene, PTFE)을 포함하는 불소수지계 바인더; 스티렌-부타디엔 고무, 아크릴로니트릴-부티디엔 고무, 스티렌-이소프렌 고무를 포함하는 고무계 바인더; 카르복시메틸셀룰로우즈(CMC), 전분, 히드 록시프로필셀룰로우즈, 재생 셀룰로우즈를 포함하는 셀룰로오스계 바인더; 폴리 알코올계 바인더; 폴리에틸렌, 폴리프로필렌를 포함하는 폴리 올레핀계 바인더; 폴리이미드계 바인더, 폴리 에스테르계 바인더, 실란계 바인더; 아크릴레이트계 바인더 또는 아크릴레이트계 공중합체 바인더;로 이루어진 군에서 선택된 1종 또는 2종 이상의 혼합물이거나 공중합체일 수 있으나, 이에 제한되지 않는다.The binder applicable to the present invention may be all binders known in the art, and specifically, a fluororesin-based binder including polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE) ; Rubber-based binders including styrene-butadiene rubber, acrylonitrile-butadiene rubber and styrene-isoprene rubber; Cellulose binders including carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose; Poly alcohol-based binders; Polyolefin-based binders including polyethylene and polypropylene; Polyimide binders, polyester binders, silane binders; An acrylate-based binder or an acrylate-based copolymer binder; may be one or a mixture of two or more selected from the group consisting of, but is not limited thereto.
상기 바인더는 전극 활물질층 형성용 조성물 총 중량에 대하여 1 내지 20 중량%로 포함되며, 바람직하게는 5 내지 15 중량%로 포함된다. 상기 바인더가 1 중량% 미만으로 포함되면 전극의 물리적 성질이 저하되어 리튬망간 산화물과 도전재가 탈락할 수 있고, 20 중량%를 초과하여 포함되면 리튬망간 산화물과 도전재의 비율이 상대적으로 감소되어 전지 용량이 감소할 수 있다.The binder is included in an amount of 1 to 20% by weight, preferably 5 to 15% by weight, based on the total weight of the composition for forming an electrode active material layer. When the binder is included in less than 1% by weight, the physical properties of the electrode may be lowered, so that the lithium manganese oxide and the conductive material may be dropped. When the binder is included in an amount of more than 20% by weight, the ratio of the lithium manganese oxide and the conductive material may be relatively reduced. This can be reduced.
상기 전극 활물질층 형성용 조성물의 혼합은 통상의 혼합기, 예컨대 레이트스 믹서, 고속 전단 믹서, 호모 믹서 등을 이용하여 통상의 방법으로 교반할 수 있다.Mixing of the composition for forming an electrode active material layer can be stirred by a conventional method using a conventional mixer, such as a latex mixer, a high speed shear mixer, a homo mixer, and the like.
또한, 상기 전극 활물질층 형성용 조성물은 슬러리 상태로 집전체 상에 도포시켜 전극을 제조할 수 있다.In addition, the electrode active material layer-forming composition may be coated on a current collector in a slurry state to prepare an electrode.
상기 조성물을 슬러리 상태로 제조하기 위하여 사용되는 용매는 건조가 용이해야 하며, 바인더를 잘 용해시킬 수 있되, 리튬망간 산화물 및 도전재는 용해시키지 않고 분산 상태로 유지시킬 수 있는 것이 가장 바람직하다. The solvent used to prepare the composition in the slurry state should be easy to dry, it is possible to dissolve the binder well, it is most preferable that the lithium manganese oxide and the conductive material can be maintained in a dispersed state without dissolving.
본 발명에 따른 용매는 물 또는 유기 용매가 가능하며, 상기 유기 용매는 디메틸포름아미드, 이소프로필알콜, 아세토니트릴, 메탄올, 에탄올, 테트라하이드로퓨란 군으로부터 선택되는 1종 이상을 포함하는 유기 용매가 적용 가능하다.The solvent according to the present invention may be water or an organic solvent, and the organic solvent is an organic solvent including at least one selected from the group consisting of dimethylformamide, isopropyl alcohol, acetonitrile, methanol, ethanol, and tetrahydrofuran. It is possible.
상기 슬러리는 슬러리의 점도 및 형성하고자 하는 전극의 두께에 따라 적절한 두께로 집전체에 코팅될 수 있으며, 바람직하게는 10 내지 300μm 범위 내에서 적절히 선택할 수 있다.The slurry may be coated on the current collector in an appropriate thickness according to the viscosity of the slurry and the thickness of the electrode to be formed, preferably, may be appropriately selected within the range of 10 to 300μm.
상기 슬러리를 집전체 상에 코팅하는 방법으로 그 제한은 없으며, 예컨대, 닥터 블레이드 코팅(Doctor blade coating), 딥 코팅(Dip coating), 그라비어 코팅(Gravure coating), 슬릿 다이 코팅(Slit die coating), 스핀 코팅(Spin coating), 콤마 코팅(Comma coating), 바 코팅(Bar coating), 리버스 롤 코팅(Reverse roll coating), 스크린 코팅(Screen coating), 캡 코팅(Cap coating) 방법 등을 수행하여 제조할 수 있다.There is no limitation to the method of coating the slurry on the current collector, for example, doctor blade coating (Dip coating), dip coating (gravure coating), slit die coating (Slit die coating), Spin coating, comma coating, bar coating, reverse roll coating, screen coating, cap coating, etc. Can be.
상기 슬러리의 코팅을 진행한 후 용매 또는 물을 제거하기 위한 건조 조건은 일반적으로 40 내지 150℃의 온도로 건조하며, 건조시간은 통상적으로 10분 이상 또는 overnight 로 진행할 수 있다.Drying conditions for removing the solvent or water after the coating of the slurry is generally dried at a temperature of 40 to 150 ℃, the drying time can be usually carried out for 10 minutes or more overnight.
상기 집전체는 일반적으로 3 내지 500μm의 두께로 만들 수 있고, 전지에 화학적 변화를 유발하지 않으면서 높은 도전성을 가지는 것이라면 특히 제한하 지 않는다. 예컨대 스테인레스 스틸, 알루미늄, 구리, 니켈, 티타늄 등의 전도성 금속을 사용할 수 있고, 바람직하게는 니켈 또는 알루미늄 집전체를 사용할 수 있다. 이러한 집전체는 필름, 시트, 호일, 네트, 다공질체, 발포체 또는 부직포체 등 다양한 형태가 가능하다.The current collector may generally be made to a thickness of 3 to 500μm, and is not particularly limited as long as it has high conductivity without causing chemical change in the battery. For example, a conductive metal such as stainless steel, aluminum, copper, nickel, titanium, or the like may be used, and nickel or an aluminum current collector may be preferably used. The current collector may be in various forms such as film, sheet, foil, net, porous body, foam or nonwoven fabric.
상기 (2)단계는 전도성 고분자 단량체 및 산을 혼합하여 프로톤화된 전도성 고분자 단량체 용액을 제조하는 단계이다.Step (2) is a step of preparing a protonated conductive polymer monomer solution by mixing a conductive polymer monomer and an acid.
본 발명에서 상기 전도성 고분자 단량체는 아닐린 단량체, 피롤 단량체, 아세틸렌 단량체, 티오펜 단량체 및 파라페닐렌 단량체로 이루어진 군으로부터 선택되는 1종 이상을 포함하며, 바람직하게는 아닐린 단량체를 포함한다.In the present invention, the conductive polymer monomer includes at least one selected from the group consisting of aniline monomers, pyrrole monomers, acetylene monomers, thiophene monomers and paraphenylene monomers, and preferably includes aniline monomers.
상기 산은 그 종류를 특별히 한정하는 것은 아니나, 염산, 질산 및 황산으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것이 바람직하다.Although the said acid does not specifically limit the kind, It is preferable to contain 1 or more types chosen from the group which consists of hydrochloric acid, nitric acid, and sulfuric acid.
상기 전도성 고분자 단량체 및 산은 1:1 내지 1:4의 몰비로 혼합되며, 바람직하게는 1:1 내지 1:2의 몰비로 혼합된다.The conductive polymer monomer and the acid are mixed in a molar ratio of 1: 1 to 1: 4, preferably in a molar ratio of 1: 1 to 1: 2.
상기 산의 농도는 0.01mM 내지 4M 일 수 있으며, 바람직하게는 0.1mM 내지 0.2M일 수 있다.The concentration of the acid may be 0.01mM to 4M, preferably 0.1mM to 0.2M.
상기 전도성 고분자 단량체 용액 및 산의 혼합을 통하여 전도성 고분자 단량체는 프로톤화(protonated)되어 (+) 전하를 갖게 된다.Through the mixing of the conductive polymer monomer solution and the acid, the conductive polymer monomer is protonated to have a positive charge.
상기 (3)단계는 상기 (1)단계에서 제조한 전극을 상기 (2)단계에서 제조한 프로톤화된 전도성 고분자 단량체 용액에 침지(soaking)시키는 단계이며, 상기 침지를 통하여 최종적으로 전도성 고분자가 코팅된 전극이 제조되는 단계이다. 구체적으로, 상기 전도성 고분자의 코팅은 집전체 상에 형성된 전극 활물질층에 코팅된 것이라 할 수 있다.Step (3) is a step of soaking the electrode prepared in step (1) in the protonated conductive polymer monomer solution prepared in step (2), and finally the conductive polymer is coated through the immersion. The prepared electrode is prepared. Specifically, the coating of the conductive polymer may be said to be coated on the electrode active material layer formed on the current collector.
일반적으로 전극에 전도성 고분자를 코팅시키거나, 전극 활물질에 전도성 고분자를 코팅시키기 위해서는 전극 활물질 표면을 (-) 전하가 되도록 처리한 뒤 프로톤화된 전도성 고분자와 정전기적 인력으로 결합을 시키고, 이후 중합 개시제 또는 산화제를 첨가하여 고분자화 반응(polymerization)을 진행하여 전도성 고분자를 코팅시킨다.In general, in order to coat the conductive polymer on the electrode or to coat the conductive polymer on the electrode active material, the surface of the electrode active material is treated with a negative charge, and then the protonated conductive polymer is bonded with electrostatic attraction. Alternatively, an oxidizing agent is added to polymerize the conductive polymer.
그러나, 본 발명에서는 전극을 프로톤화된 전도성 고분자 단량체 용액에 침지시키는 과정만으로도 고분자화 반응을 진행할 수 있어 전도성 고분자로 전극 표면을 코팅시킬 수 있다.However, in the present invention, the polymerization reaction can be performed only by immersing the electrode in the protonated conductive polymer monomer solution, thereby coating the electrode surface with the conductive polymer.
상기 리튬망간 산화물(LiMn2O4)은 산에 노출되면 리튬 이온이 용출되면서 Mn3+ 이온이 생성되며, 상기 Mn3+ 이온은 표준환원전위가 +1.51 eV(표준 수소 전극 기준 (vs. NHE))로 산화성을 띈다. 즉, 상기 (2)단계에서 제조한 프로톤화된 전도성 고분자 단량체 용액에 상기 (1)단계에서 제조한 리튬망간 산화물을 포함하는 전극을 침지시키면, 리튬망간 산화물 표면에서 Mn3+ 이온이 발생하게 되고, 상기 Mn3+ 이온이 전도성 고분자 중합에서의 개시제 또는 산화제 역할을 하게 된다(식 1 및 2). 상기 (2)단계에서 제조한 용액은 전도성 고분자 단량체가 프로톤화되어 있으므로 리튬망간 산화물 표면에서 발생한 Mn3+ 이온에 의해 프로톤화된 전도성 고분자 단량체가 산화되면서 상기 단량체의 중합이 시작된다. The lithium manganese oxide (LiMn 2 O 4) as the lithium ions are eluted when exposed to acid and Mn 3+ ions are generated, the Mn 3+ ion has a standard reduction potential of +1.51 eV (based on the standard hydrogen electrode (vs. NHE It is oxidizing with)). That is, when the electrode containing the lithium manganese oxide prepared in step (1) is immersed in the protonated conductive polymer monomer solution prepared in step (2), Mn 3+ ions are generated on the surface of the lithium manganese oxide The Mn 3+ ions serve as an initiator or an oxidizer in the conductive polymer polymerization (
LiMn2O4 + 4H+ → Li+ + Mn3+ +MnO2 + H2O (식 1)LiMn 2 O 4 + 4H + → Li + + Mn 3+ + MnO 2 + H 2 O (Equation 1)
Mn3+ + e- → Mn2+, E0 = +1.51 eV (vs. NHE) (식 2) Mn 3+ + e - → Mn 2+ ,
즉, 본 발명은 전극 활물질 표면을 (-) 전하가 되도록 처리 하지 않아도 되며, 중합 개시제 또는 산화제를 사용하지 않아도 되므로, 간단한 방법으로 전극 표면을 전도성 고분자로 코팅할 수 있다.That is, the present invention does not need to treat the surface of the electrode active material to be a (-) charge, and does not need to use a polymerization initiator or an oxidizing agent, it is possible to coat the electrode surface with a conductive polymer in a simple manner.
프로톤화된 전도성 고분자 단량체 용액에 전극을 침지시키는 시간 및 프로톤화된 전도성 고분자 단량체 용액의 농도에 따라 전도성 고분자의 코팅 두께를 조절할 수 있으며, 본 발명에서 침지 시간은 1분 내지 5시간, 바람직하게는 30분 내지 1시간이다. 상기 침지 시간이 1분 미만이면 전도성 고분자 코팅이 지나치게 얇게 되어 전기화학적 안정성 및 출력특성이 향상된 전극을 얻을 수 없으며, 5시간을 초과하면 코팅 두께가 더 이상 증가하지 않는다.The coating thickness of the conductive polymer may be adjusted according to the time of immersing the electrode in the protonated conductive polymer monomer solution and the concentration of the protonated conductive polymer monomer solution. In the present invention, the immersion time is 1 minute to 5 hours, preferably 30 minutes to 1 hour. If the immersion time is less than 1 minute, the conductive polymer coating becomes too thin to obtain an electrode with improved electrochemical stability and output characteristics, and when the immersion time exceeds 5 hours, the coating thickness no longer increases.
또한, 본 발명에서 프로톤화된 전도성 고분자 단량체 용액의 농도는 0.01mM 내지 1M, 바람직하게는 0.1mM 내지 0.1M이다. 상기 용액의 농도가 0.01mM 미만이면 전도성 고분자 코팅이 거의 이루어지지 않으며, 1M을 초과하면 코팅 속도가 너무 빨라서 전도성 고분자의 코팅 두께를 정확히 제어하기 어렵다.In addition, the concentration of the protonated conductive polymer monomer solution in the present invention is 0.01mM to 1M, preferably 0.1mM to 0.1M. When the concentration of the solution is less than 0.01mM, the conductive polymer coating is hardly made. If the concentration of the solution exceeds 1M, the coating speed is too fast, and it is difficult to accurately control the coating thickness of the conductive polymer.
상기 침지 시간 및 프로톤화된 전도성 고분자 단량체 용액의 농도에 따라 코팅되는 전도성 고분자의 두께는 1 내지 50nm이며, 바람직하게는 3 내지 10nm이다. 상기 코팅 두께가 1nm 미만이면 전도성 고분자 코팅 두께가 지나치게 얇아 전극의 전기화학적 안정성 및 출력 특성 향상을 기대하기 어려우며, 50nm를 초과하면 코팅 두께가 지나치게 두꺼워 전극 활물질층의 표면까지의 전해질 이온 전달 능력이 현저하게 감소하여 전극의 전기화학적 성능 및 출력 특성이 감소할 수 있다. The thickness of the conductive polymer to be coated is 1 to 50 nm, preferably 3 to 10 nm, depending on the immersion time and the concentration of the protonated conductive polymer monomer solution. If the thickness of the coating is less than 1 nm, the thickness of the conductive polymer coating is too thin, so it is difficult to expect the improvement of the electrochemical stability and the output characteristics of the electrode. If the thickness is greater than 50 nm, the coating thickness is too thick. To reduce the electrochemical performance and output characteristics of the electrode.
상기 침지 후에 전도성 고분자가 코팅된 전극을 세척 및 건조하여 최종적으로 전도성 고분자가 코팅된 전극을 얻을 수 있다.After the immersion, the electrode coated with the conductive polymer may be washed and dried to finally obtain the electrode coated with the conductive polymer.
상기 전도성 고분자가 코팅된 전극은 양극으로 사용되며, 바람직하게는 커패시터용 양극 또는 리튬전지용 양극으로 사용될 수 있다.The electrode coated with the conductive polymer is used as a positive electrode, and preferably used as a positive electrode for a capacitor or a positive electrode for a lithium battery.
이하, 본 발명의 실시예를 참조하여 설명하지만, 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범주가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described with reference to Examples, but the following Examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.
실시예 1. 전극 제조Example 1. Electrode Preparation
리튬망간 산화물(LiMn2O4), 도전재 및 바인더를 85:10:5의 중량비로 혼합한 혼합물을 NMP(N-methyl-2-pyrrolidone)에 용해하여 슬러리를 제조한 후, 20μm 두께의 니켈 집전체에 코팅하였다. 그 후 120℃의 온도로 20분 동안 건조하여 전극을 제조하였다.20 μm-thick nickel was prepared by dissolving a mixture of lithium manganese oxide (LiMn 2 O 4 ), a conductive material and a binder in a weight ratio of 85: 10: 5 in NMP (N-methyl-2-pyrrolidone). The current collector was coated. Thereafter, the electrode was manufactured by drying at a temperature of 120 ° C. for 20 minutes.
상기 도전재로 아세틸렌 블랙(acetylene black)을 사용하였으며, 바인더로 폴리비닐리덴 플루오라이드(polyvinylidene fluoride)를 사용하였다.Acetylene black was used as the conductive material, and polyvinylidene fluoride was used as the binder.
아닐린 단량체 및 염산을 1:2의 몰비로 혼합한 용액을 준비하였다. 상기 용액 중 아닐린 단량체의 농도는 0.5mM이며, 염산의 농도는 1mM이었다. 상기 용액에 상기 전극을 30분 동안 침지(soaking)시켜 폴리아닐린이 코팅된 전극을 제조하였다.The solution which mixed aniline monomer and hydrochloric acid in the molar ratio of 1: 2 was prepared. The concentration of aniline monomer in the solution was 0.5 mM and the concentration of hydrochloric acid was 1 mM. The electrode was soaked in the solution for 30 minutes to prepare an electrode coated with polyaniline.
상기 전극의 표면을 관찰한 결과, 리튬망간 산화물 표면에 폴리아닐린이 20nm 두께로 고르게 코팅된 것을 확인하였다(도 1 및 도 2).As a result of observing the surface of the electrode, it was confirmed that the polyaniline was evenly coated with a thickness of 20 nm on the surface of the lithium manganese oxide (FIGS. 1 and 2).
비교예 1. 전극 제조Comparative Example 1. Electrode Preparation
리튬망간 산화물(LiMn2O4), 도전재 및 바인더를 85:10:5의 중량비로 혼합한 혼합물을 NMP(N-methyl-2-pyrrolidone)에 용해하여 슬러리를 제조한 후, 20μm 두께의 니켈 호일의 집전체에 코팅하였다. 그 후 120℃의 온도로 20분 동안 건조하여 전극을 제조하였다(도 3 및 도 4).20 μm-thick nickel was prepared by dissolving a mixture of lithium manganese oxide (LiMn 2 O 4 ), a conductive material and a binder in a weight ratio of 85: 10: 5 in NMP (N-methyl-2-pyrrolidone). The current collector of the foil was coated. Thereafter, the electrode was prepared by drying at a temperature of 120 ° C. for 20 minutes (FIGS. 3 and 4).
상기 도전재로 아세틸렌 블랙(acetylene black)을 사용하였으며, 바인더로 폴리비닐리덴 플루오라이드(polyvinylidene fluoride)를 사용하였다.Acetylene black was used as the conductive material, and polyvinylidene fluoride was used as the binder.
실험예 1. 전극의 특성 측정Experimental Example 1. Measurement of the characteristics of the electrode
상기 실시예 1 및 비교예 1에서 제조한 전극을 양극으로 하였다. 1M LiSO4 수용액을 전해액을 사용하여 각각 3전극 정전류 충방전 특성을 평가하였다. The electrodes prepared in Example 1 and Comparative Example 1 were used as positive electrodes. Three-electrode constant current charge-discharge characteristics of the 1M LiSO 4 aqueous solution were evaluated using an electrolyte solution.
그 결과, 전도성 고분자가 코팅된 실시예 1의 전극의 용량이 10.7 A/g에서 118.2 mAh/g로 측정되었으며, 이는 전도성 고분자가 코팅되지 않은 비교예 1의 전극의 용량인 116.4 A/g보다 증가한 수치이다 (도 5). As a result, the capacity of the electrode of Example 1 coated with a conductive polymer was measured to be 118.2 mAh / g at 10.7 A / g, which was higher than that of 116.4 A / g, which is the capacity of the electrode of Comparative Example 1 not coated with a conductive polymer. Numerical value (Figure 5).
또한, 1.3 A/g에서 26.7 A/g까지 전류를 증가시켰을 때의 용량 감소 정도인 출력특성을 평가하였을 때, 전도성 고분자가 코팅된 실시예 1의 전극의 경우 93.1%를 유지하였으며, 전도성 고분자가 코팅되지 않은 비교예 1의 전극의 경우 91.4%를 유지하였다. 이는 리튬망간 산화물에 전도도가 높은 전도성 고분자가 고르게 코팅됨으로써 전하전달이 기존보다 더 원활하게 이루어졌기 때문이라고 볼 수 있다(도 6).In addition, when evaluating the output characteristics of the capacity reduction when increasing the current from 1.3 A / g to 26.7 A / g, the electrode of Example 1 coated with a conductive polymer was maintained at 93.1%, 91.4% was maintained for the uncoated electrode of Comparative Example 1. This is because the conductive polymer with high conductivity is coated evenly on the lithium manganese oxide, it can be seen that the charge transfer is made more smoothly than before (Fig. 6).
이와 함께 상기 실시예 1 및 비교예 1의 전극의 충방전 안정성 평가를 실시하였다. 충방전 속도는 각각 10.7 A/g으로 고정한 후, 충방전 횟수에 따른 상대적 용량 및 상기 전극의 cycle 안정성을 평가하였다(도 7).In addition, charge and discharge stability evaluation of the electrode of Example 1 and Comparative Example 1 was performed. The charge and discharge rates were fixed at 10.7 A / g, respectively, and the relative capacity and cycle stability of the electrode according to the number of charge and discharge cycles were evaluated (FIG. 7).
그 결과, 전도성 고분자를 코팅한 실시예 1의 전극이 7,000번째 충방전 횟수에서 초기 용량의 80.8%를 유지하였으며, 전도성 고분자를 코팅하지 않은 비교예 1의 전극의 경우 66.9%를 유지하였다. 이는 리튬망간 산화물에 코팅된 전도성 고분자가 충방전이 계속될 때 망간이 용해되는 것을 막아주기 때문이라고 볼 수 있다.As a result, the electrode of Example 1 coated with the conductive polymer maintained 80.8% of the initial capacity at the 7,000th charge and discharge cycle, and 66.9% of the electrode of Comparative Example 1 not coated with the conductive polymer. This may be because the conductive polymer coated on the lithium manganese oxide prevents manganese from dissolving when charge and discharge continue.
한편, 실시예 1의 전극의 충방전 안정성 그래프가 연속적이지 않은 계단식 그래프로 관찰되었다. 이는 3전극 측정시 상대 전극에서 나오는 수소 기체로 인하여 전해질 내 용존 수소가 포화되어 실시예 1의 전극에 기체로 맺히기 때문이다. 전극 표면이 기체로 덮이게 되면 충방전이 완전히 이루어지지 않아 용량이 감소하는 것처럼 보일 수 있다. 그러나 도 7의 그래프에서 확인할 수 있듯이, 전극에 맺힌 기체를 제거해주면 수 사이클 내 다시 회복되어 원래의 용량으로 되돌아오므로, 상기의 현상으로 인하여 전극의 충방전 안정성이 저하되는 것이라고는 볼 수 없다. On the other hand, the charge-discharge stability graph of the electrode of Example 1 was observed as a stepped graph that is not continuous. This is because dissolved hydrogen in the electrolyte saturates due to the hydrogen gas coming from the counter electrode when the three electrodes are measured and forms a gas on the electrode of Example 1. If the surface of the electrode is covered with gas, it may appear that the charge and discharge are not completely performed and the capacity decreases. However, as can be seen in the graph of FIG. 7, when the gas trapped in the electrode is removed, it recovers again within several cycles and returns to its original capacity. Therefore, the charge and discharge stability of the electrode may not be deteriorated due to the above phenomenon.
따라서, 본 발명의 전도성 고분자가 코팅된 전극 제조방법은 산화제 또는 개시제를 사용하지 않고도 전극 표면에 전도성 고분자를 코팅할 수 있어 그 방법이 매우 간단하며, 이를 통하여 전극의 전기화학적 안정성 및 출력 특성이 우수한 전극을 제공할 수 있다는 것을 알 수 있다.Therefore, the method of manufacturing an electrode coated with the conductive polymer of the present invention can coat the conductive polymer on the surface of the electrode without using an oxidizing agent or an initiator, and thus the method is very simple, and thus the electrochemical stability and output characteristics of the electrode are excellent. It can be seen that the electrode can be provided.
Claims (12)
(2)전도성 고분자 단량체 및 산을 혼합하여 프로톤화된 전도성 고분자 단량체 용액을 제조하는 단계; 및
(3)상기 전극을 상기 프로톤화된 전도성 고분자 단량체 용액에 침지(soaking)시키는 단계;를 포함하는 전도성 고분자가 코팅된 전극 제조방법.(1) preparing an electrode including lithium manganese oxide (LiMn 2 O 4 );
(2) mixing a conductive polymer monomer and an acid to prepare a protonated conductive polymer monomer solution; And
(3) soaking the electrode in the protonated conductive polymer monomer solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020180081386A KR102617869B1 (en) | 2018-07-13 | 2018-07-13 | Method for preparing electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020180081386A KR102617869B1 (en) | 2018-07-13 | 2018-07-13 | Method for preparing electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20200007359A true KR20200007359A (en) | 2020-01-22 |
| KR102617869B1 KR102617869B1 (en) | 2023-12-22 |
Family
ID=69368332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020180081386A KR102617869B1 (en) | 2018-07-13 | 2018-07-13 | Method for preparing electrode |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102617869B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3644416A4 (en) * | 2017-11-20 | 2020-11-18 | LG Chem, Ltd. | Metal oxide coated with conductive polymer, electrode for electrochemical element using same, and method for producing metal oxide coated with conductive polymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030006596A (en) * | 2001-07-13 | 2003-01-23 | 주식회사 네스캡 | Conducting polymer coated electrode of metal oxide electrochemical pseudocapacitor and method of manufacturing the same |
| KR20140119250A (en) * | 2013-03-27 | 2014-10-10 | 국립대학법인 울산과학기술대학교 산학협력단 | Positive electrode active material and method of manufacturing the same, positive electrode and method of manufacturing the same, and electrochemical device having the positive electrode |
-
2018
- 2018-07-13 KR KR1020180081386A patent/KR102617869B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030006596A (en) * | 2001-07-13 | 2003-01-23 | 주식회사 네스캡 | Conducting polymer coated electrode of metal oxide electrochemical pseudocapacitor and method of manufacturing the same |
| KR20140119250A (en) * | 2013-03-27 | 2014-10-10 | 국립대학법인 울산과학기술대학교 산학협력단 | Positive electrode active material and method of manufacturing the same, positive electrode and method of manufacturing the same, and electrochemical device having the positive electrode |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3644416A4 (en) * | 2017-11-20 | 2020-11-18 | LG Chem, Ltd. | Metal oxide coated with conductive polymer, electrode for electrochemical element using same, and method for producing metal oxide coated with conductive polymer |
| US11870062B2 (en) | 2017-11-20 | 2024-01-09 | Lg Energy Solution, Ltd. | Metal oxide coated with conductive polymer, electrode for electrochemical device comprising the same, and method of producing the metal oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102617869B1 (en) | 2023-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Highly porous polyacrylonitrile/graphene oxide membrane separator exhibiting excellent anti-self-discharge feature for high-performance lithium–sulfur batteries | |
| US9685678B2 (en) | Electrode materials with a synthetic solid electrolyte interface | |
| TWI483446B (en) | A battery collector, a battery positive electrode, a battery negative electrode, a battery, and a manufacturing method | |
| JP4593488B2 (en) | Secondary battery current collector, secondary battery positive electrode, secondary battery negative electrode, secondary battery, and production method thereof | |
| JP4909443B2 (en) | Secondary battery current collector, secondary battery positive electrode and secondary battery | |
| WO2006008930A1 (en) | Negative electrode material for lithium secondary battery, method for producing same, negative electrode for lithium secondary battery using same and lithium secondary battery | |
| KR101910391B1 (en) | Fiber-typed Supercapacitors Using Fiber Bundles and Method for Fabricating the Same | |
| Ding et al. | Polyaniline@ spherical ordered mesoporous carbon/sulfur nanocomposites for high-performance lithium-sulfur batteries | |
| JP7128303B2 (en) | Sulfur-carbon composite, method for producing the same, and lithium secondary battery containing the same | |
| TW201904112A (en) | Positive electrode for lithium ion secondary battery and lithium ion secondary battery | |
| KR100551005B1 (en) | Positive electrode for lithium-sulfur battery and lithium-sulfur battery comprising same | |
| CN107925057A (en) | Anode of secondary cell, its preparation method and the lithium secondary battery for including the cathode | |
| JP2017130557A (en) | Method of pre-doping lithium | |
| JP2020523772A (en) | Electrode and lithium secondary battery including the same | |
| JP2010080221A (en) | Negative electrode material, and negative electrode for battery | |
| JP6529700B1 (en) | Current collector for power storage device, method for producing the same, and coating liquid used for the production | |
| WO2019108027A1 (en) | Method for manufacturing electrode for secondary battery | |
| KR102617869B1 (en) | Method for preparing electrode | |
| WO2017177960A1 (en) | Electrolyte solution, battery, and battery pack | |
| KR20200050560A (en) | A anode for lithium secondary battery, the manufacturing method of the same and lithium secondary battery comprising the same | |
| JP7080347B2 (en) | Sulfur-carbon composite, this manufacturing method, positive electrode for lithium-sulfur battery including this and lithium-sulfur battery | |
| CN112054158A (en) | Method for preparing electrode for secondary battery and secondary battery comprising the same | |
| WO2019098546A2 (en) | Metal oxide coated with conductive polymer, electrode for electrochemical element using same, and method for producing metal oxide coated with conductive polymer | |
| KR102589078B1 (en) | Positive electrode slurry using low boiling point/non-aromatic solvent, secondary battery positive electrode containing the same, and method for manufacturing the same | |
| KR20220163580A (en) | Negative electrode for lithium secondary battery and lithium secondary battery comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |