CN116918093A - Electrode for electrochemical device and electrochemical device including the same - Google Patents
Electrode for electrochemical device and electrochemical device including the same Download PDFInfo
- Publication number
- CN116918093A CN116918093A CN202280019145.9A CN202280019145A CN116918093A CN 116918093 A CN116918093 A CN 116918093A CN 202280019145 A CN202280019145 A CN 202280019145A CN 116918093 A CN116918093 A CN 116918093A
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- electrode
- electrochemical device
- conductive polymer
- polymer layer
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- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
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- 230000001186 cumulative effect Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- BLBBMBKUUHYSMI-UHFFFAOYSA-N furan-2,3,4,5-tetrol Chemical compound OC=1OC(O)=C(O)C=1O BLBBMBKUUHYSMI-UHFFFAOYSA-N 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004750 melt-blown nonwoven Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001523 phosphate polymer Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910006636 γ-AlOOH Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present disclosure provides an electrode for an electrochemical device including a conductive polymer layer on at least one surface of an electrode current collector; and an electrode active material layer on an upper surface of the conductive polymer layer and including an electrode active material and a binder polymer, wherein the conductive polymer layer includes a poly (thiophene) -based polymer represented by chemical formula 1 in the detailed description.
Description
Technical Field
The present application claims the benefits of korean patent application No. 2021-0110653 submitted at the korean intellectual property office at 9 of 2021 and korean patent application No. 2022-0110884 submitted at the korean intellectual property office at 9 of 2022, the contents of which are incorporated herein by reference in their entireties.
The present disclosure relates to an electrode for an electrochemical device and an electrochemical device including the same. More particularly, the present disclosure relates to an electrode for an electrochemical device having improved safety, and an electrochemical device including the same.
Background
Recently, energy storage technology has received increasing attention. Efforts for developing electrochemical devices have been increasingly implemented because the application of energy storage technology has been expanded to energy sources for mobile phones, video cameras and notebook PCs, and even to energy sources for electric automobiles.
Such an electrochemical device may be largely divided into a positive electrode, a negative electrode, a separator, and an electrolyte. However, the electrochemical device may burn or explode due to overcharge, high temperature exposure, external impact, or the like. If the electrochemical device is overcharged or exposed to a high temperature to raise the internal temperature of the battery and shrink the separator, or if the internal structure of the electrochemical device is damaged by external impact, a short circuit phenomenon occurs where the positive electrode contacts the negative electrode, resulting in thermal runaway.
When the short circuit phenomenon occurs, the movement of electrons including lithium ions is concentrated through the portion where the positive electrode and the negative electrode are in direct contact with each other, thereby promoting heat generation inside the battery. As a result, it is known that the risk of volume expansion and combustion due to gas generation increases.
Therefore, there is a great need for a technology that can reduce the risk of battery burning due to the short circuit phenomenon.
Disclosure of Invention
Technical problem
The present disclosure provides an electrode for an electrochemical device having improved safety, and an electrochemical device including the same.
Technical proposal
According to one aspect of the present disclosure, an electrode for an electrochemical device is provided.
The electrode for an electrochemical device according to the first embodiment includes:
An electrode current collector;
a conductive polymer layer on at least one surface of the electrode current collector; and
an electrode active material layer on an upper surface of the conductive polymer layer and including an electrode active material and a binder polymer,
wherein the conductive polymer layer comprises a poly (thiophene) (poly (thiophene)) based polymer represented by chemical formula 1.
The second embodiment is the electrode for an electrochemical device according to the first embodiment, wherein the adhesive strength between the conductive polymer layer and the electrode current collector may be 200gf/20mm or more.
A third embodiment is the electrode for an electrochemical device according to the first or second embodiment, wherein an interfacial resistance (interface resistance) between the conductive polymer layer and the electrode active material layer may be 3.0 ohm-cm 2 Or smaller.
A fourth embodiment is the electrode for an electrochemical device according to any one of the first to third embodiments, wherein R 1 And R is 2 Sum of carbon atoms of R 3 And R is 4 At least one of the total number of carbon atoms of (c) may be 5 or more.
A fifth embodiment is the electrode for an electrochemical device according to any one of the first to fourth embodiments, wherein the m or the n may be 0.
A sixth embodiment is the electrode for an electrochemical device according to any one of the first to fifth embodiments, wherein the conductive polymer layer may have a thickness of 0.1 μm to 8 μm.
A seventh embodiment is the electrode for an electrochemical device according to any one of the first to sixth embodiments, wherein the conductive polymer layer may further include a poly (aniline) based polymer; poly (pyrrrole) based polymers; poly (phenylene) (poly (phenylene)) based polymers; poly (acetylene) (poly (acetylene)) based polymers; their derivatives; or two or more thereof.
An eighth embodiment is the electrode for an electrochemical device according to any one of the first to seventh embodiments, wherein the electrode for an electrochemical device may be a positive electrode.
In order to achieve the above object, according to another aspect of the present disclosure, there is provided an electrochemical device including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode,
wherein the positive electrode or the negative electrode includes the electrode for an electrochemical device according to any one of the first to eighth embodiments.
Advantageous effects
An electrode for an electrochemical device according to one embodiment of the present disclosure is configured to position a conductive polymer layer between an electrode current collector and an electrode active material layer such that it can prevent direct contact between the electrode current collector when a short circuit occurs while not interfering with a conductive path between the electrode current collector and the electrode active material layer during normal operation of the battery.
Since the conductive polymer layer located between the electrode current collector and the electrode active material layer serves as a resistive layer, the electrode for an electrochemical device according to the embodiments of the present disclosure may increase short-circuit resistance and prevent rapid flow of short-circuit current to ensure safety.
Drawings
The following drawings, which are attached hereto, illustrate preferred embodiments of the present invention and together with the description of the invention given above, serve to further understand the technical idea of the invention. The present disclosure should not be construed as limited to the embodiments as shown in the drawings.
Fig. 1 is a diagram schematically illustrating an electrode for an electrochemical device according to one embodiment of the present invention.
Detailed Description
Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Before the description, it is to be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present disclosure on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation.
Accordingly, the embodiments described herein and the configurations shown in the drawings are only the most preferred embodiments of the present disclosure, and thus it should be understood that there may be various equivalents and modifications that may replace these embodiments and configurations when submitting the present application, and the scope of the present application is not limited to the following embodiments.
An electrode for an electrochemical device according to an embodiment of the present disclosure includes:
an electrode current collector;
a conductive polymer layer on at least one surface of the electrode current collector; and
an electrode active material layer on an upper surface of the conductive polymer layer and including an electrode active material and a binder polymer,
wherein the conductive polymer layer comprises a poly (thiophene) (poly (thiophene)) based polymer represented by the following chemical formula 1:
[ chemical formula 1]
Wherein, in the chemical formula 1,
R 1 、R 2 、R 3 and R 4 Each independently is hydrogen or substituted or unsubstituted alkyl having 1 to 20 carbon atoms, R 1 And R is 2 Sum of carbon atoms of R 3 And R is 4 At least one of the total number of carbon atoms of (3) or more, m and n are each independently an integer of 0 to 20,000, and m+n > 0.
In chemical formula 1, when m and n are each an integer of 1 or more, the monomer represented by the repeating unit m and the monomer represented by the repeating unit n are to show structures different from each other.
In one embodiment of the present disclosure, when m and n in chemical formula 1 are each an integer of 1 or more, the polythiophene-based polymer represented by chemical formula 1 may be an alternating polymer, a random polymer, or a block polymer of a monomer represented by a repeating unit m and a monomer represented by a repeating unit n, but is not limited thereto.
Fig. 1 is a diagram schematically illustrating an electrode for an electrochemical device according to one embodiment of the present disclosure.
Referring to fig. 1, an electrode 1 for an electrochemical device according to an embodiment of the present disclosure includes an electrode current collector 10.
The electrode current collector 10 may be used without particular limitation as long as it has conductivity and does not cause chemical changes in the electrochemical device. For example, in one embodiment of the present disclosure, as the electrode current collector 10, copper may be used; stainless steel; aluminum; nickel; titanium; calcining the carbon; copper, aluminum or stainless steel having a surface treated with carbon, nickel, titanium, silver, or the like; aluminum-cadmium alloy; and the like. The current collector may form a random body on its surface to enhance the bonding strength of the active material, and it may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric structure.
In one embodiment of the present disclosure, when the electrode 1 for an electrochemical device is a positive electrode, the electrode current collector 10 may include stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel having a surface treated with carbon, nickel, titanium, silver, chromium, and the like.
In another embodiment of the present disclosure, when the electrode 1 for an electrochemical device is a negative electrode, the electrode current collector 10 may include copper, stainless steel, nickel, titanium, calcined carbon, or aluminum or stainless steel having a surface treated with carbon, nickel, titanium, silver, chromium, or the like, an aluminum-cadmium alloy, and the like.
In one embodiment of the present disclosure, the electrode current collector 10 may have a thickness of 3 μm to 500 μm, for example, 10 μm to 50 μm, or 10 μm to 20 μm, but is not particularly limited thereto.
Referring to fig. 1, an electrode 1 for an electrochemical device according to one embodiment of the present disclosure forms a conductive polymer layer 20 on at least one surface of an electrode current collector 10.
If the electrochemical device is overcharged or exposed to high temperature and the internal temperature of the electrochemical device increases, the separator contracts, which may cause a short circuit phenomenon between the positive electrode and the negative electrode. Alternatively, the internal structure of the electrochemical device may be damaged by external impact, which may cause a short circuit (short circuit) between the positive electrode and the negative electrode.
Such a short circuit includes a soft (soft) short circuit caused by contact between the positive electrode active material and the negative electrode active material, or a hard (hard) short circuit caused by direct contact between the positive electrode current collector and the negative electrode current collector, or between the positive electrode current collector and the negative electrode active material, or between the negative electrode current collector and the positive electrode active material. Hard shorts have lower short circuit resistance, resulting in greater heat generation, which is a serious threat to the safety of the battery.
The conductive polymer layer 20 is formed on at least one surface of the electrode collector 10 and serves as a protective film for the electrode collector 10 when a short circuit phenomenon occurs. The conductive polymer layer 20 is formed on at least one surface of the electrode collector 10, and thus can prevent the electrode collector 10 from directly contacting an opposite electrode collector or an opposite electrode active material. Thus, hard short circuit can be prevented from occurring.
In order for such a conductive polymer layer 20 to serve as a protective film for the electrode collector 10, the conductive polymer layer 20 should not be separated from the electrode collector 10 even when the conductive polymer layer 20 is strongly bonded to the electrode collector 10 and a short circuit phenomenon occurs. If the conductive polymer layer 20 is easily peeled off from the electrode collector 10, it cannot serve as a protective film for the electrode collector 10 when a short circuit phenomenon occurs.
In one embodiment of the present disclosure, the adhesive strength between the conductive polymer layer 20 and the electrode current collector 10 may be 200gf/20mm or more, specifically 210gf/20mm or more. The upper limit of the adhesive strength between the conductive polymer layer and the electrode current collector is not particularly limited, but may be, for example, 400gf/20mm or less, or 350gf/20mm or less. When the adhesive strength between the conductive polymer layer 20 and the electrode collector 10 satisfies the above range, the conductive polymer layer 20 is not detached from the electrode collector 10 when a short circuit phenomenon occurs, but can be easily strongly bonded to the electrode collector 10, which makes it easier for the conductive polymer layer 20 to function as a protective film for the electrode collector 10.
The adhesive strength between the conductive polymer layer 20 and the electrode collector 10 can be known by measuring strength when the electrode collector 10 having the conductive polymer layer 20 formed thereon is attached and fixed to a glass plate using a double-sided adhesive tape, and then the electrode collector 10 is peeled off at an angle of 90 deg. at a speed of 20mm/min at 25 deg.
In addition, the conductive polymer layer 20 is located between the electrode collector 10 and an electrode active material layer, which will be described later, and thus can increase the interfacial resistance between the electrode collector 10 and the electrode active material layer compared to the case where the electrode collector 10 and the electrode active material layer are in direct contact with each other, thereby preventing the electrochemical device from being burned due to the interfacial resistance even if a short circuit phenomenon occurs.
In one embodiment of the present disclosure, the interfacial resistance between the conductive polymer layer 20 and the electrode active material layer may be increased by 0.1% to 1000%, or 1% to 500% as compared to the conventional case where the current collector and the electrode active material layer are in direct contact with each other.
In one embodiment of the present disclosure, the interfacial resistance (interface resistance) between the conductive polymer layer 20 and the electrode active material layer may be 3.0 ohm-cm 2 Or less, 2.5ohm cm 2 Or less, or 0.01ohm cm 2 To 2.5ohm cm 2 . When the interfacial resistance between the conductive polymer layer 20 and the electrode active material layer satisfies the aboveIn the range, it can make it easy to prevent the electrochemical device from burning when a short circuit phenomenon occurs, and even at the same time, can secure cycle characteristics. For example, it may facilitate preventing the electrochemical device from burning when a short circuit occurs, while preventing the cycle efficiency from being less than 80%.
The interfacial resistance (interface resistance) between the conductive polymer layer 20 and the electrode active material layer can be measured using a multi-probe tester.
Further, the conductive polymer layer 20 includes a polymer exhibiting conductivity by interacting with a salt in the electrolyte, thereby enabling a conductive network between the electrode current collector 10 and an electrode active material layer described later. Accordingly, when the battery is operated normally, the performance of the electrode can be maintained even when the conductive polymer layer 20 is present between the electrode current collector 10 and an electrode active material layer, which will be described later.
In one embodiment of the present disclosure, in chemical formula 1 representing the polythiophene-based polymer included in the conductive polymer layer, R 1 And R is 2 Sum of carbon atoms of R 3 And R is 4 At least one of the total number of carbon atoms of (c) is 5 or more, for example 6 to 20, 7 to 20, 8 to 15, or 8 to 10. When R is 1 And R is 2 Sum of carbon atoms of R 3 And R is 4 When at least one of the total numbers of carbon atoms of (c) is within the above range, it may exhibit the beneficial effect that the life of a battery using the same may be further improved while excellently maintaining the adhesive strength between the conductive polymer layer using the same and the electrode current collector, but the present disclosure is not limited thereto.
In one embodiment of the present disclosure, in chemical formula 1 representing the polythiophene-based polymer included in the conductive polymer layer, m or n may be 0. When m or n is 0, it may exhibit the beneficial effect that the life of a battery using the same may be further improved while excellently maintaining the adhesive strength between the conductive polymer layer using the same and the electrode current collector, but the present disclosure is not limited thereto.
In one embodiment of the present disclosure, the weight average molecular weight (Mw) of the conductive polymer may be, for example, 10,000g/mol to 100,000g/mol. Specifically, the weight average molecular weight (Mw) of the conductive polymer may be 10,000g/mol to 80,000g/mol or 30,000g/mol to 60,000g/mol. When the weight average molecular weight of the conductive polymer is within the above range, there may be a beneficial effect in terms of adhesion strength and interfacial resistance between the conductive polymer layer and the electrode active material layer, but the present disclosure is not limited thereto.
As used herein, the weight average molecular weight of the conductive polymer may be a value measured using gel permeation chromatography. Specifically, the weight average molecular weight may be a value measured using PL GPC220 (Agilent Technologies) under the following conditions.
-column: PL oxide (Polymer Laboratories)
-a solvent: TCB (trichlorobenzene)
-flow rate: 1.0ml/min
Sample concentration: 1.0mg/ml
Injection amount: 200 μl
Column temperature: 160 DEG C
-a detector: agilent high temperature RI detector
-criteria: polystyrene (correcting by cubic function)
In one embodiment of the present disclosure, the thickness of the conductive polymer layer may be, for example, 0.1 μm to 15 μm, specifically 0.1 μm to 10 μm, 0.1 μm to 8 μm, 0.5 μm to 10 μm, 0.5 μm to 8 μm, 0.5 μm to 5 μm, 1 μm to 5 μm, or 1 μm to 3 μm. When the thickness of the conductive polymer layer is within the above range, it may exhibit advantageous effects in terms of improving interface resistance between the conductive polymer layer and the electrode current collector and thus improving life characteristics of the battery, but the present disclosure is not limited thereto.
As used herein, the "thickness" of the conductive polymer layer may represent a value measured by known methods for measuring thickness. The method for measuring thickness may be, but is not limited to, a value measured using, for example, a thickness measurement system (Mitutoyo VL-50S-B).
In one embodiment of the present disclosure, the conductive polymer layer 20 may further include a poly (aniline) based polymer in addition to the polythiophene based polymer as the conductive polymer; poly (pyrrrole) based polymers; poly (phenylene) (poly (phenylene)) based polymers; poly (acetylene) (poly (acetylene)) based polymers; their derivatives; or two or more thereof.
The poly (aniline) based polymer is not particularly limited as long as it includes an aniline repeating unit. For example, it may comprise a homopolymer consisting of only aniline repeat units, or may comprise a copolymer of aniline monomers with other monomers.
The poly (pyrrole) -based polymer is not particularly limited as long as it includes pyrrole repeating units. For example, it may comprise a homopolymer consisting of only pyrrole repeating units, or may comprise a copolymer of pyrrole monomer with another monomer.
The poly (pyrrole) -based polymer may include a structure represented by the following chemical formula 2 or 3:
[ chemical formula 2]
Wherein, in the chemical formula 2,
R 1 and R is 2 Each independently is hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and
m is 1 to 20,000.
[ chemical formula 3]
Wherein, in the chemical formula 3,
x is
Q is oxygen or sulfur and is preferably selected from the group consisting of,
r is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms,
p is a natural number of 1 or more, and
n is 1 to 20,000.
Throughout this specification, "substituted" refers to the use of alkyl groups such as methyl, ethyl, isopropyl, and butyl; alkoxy groups such as methoxy and ethoxy; an aromatic hydrocarbon group; an alcohol group; a carboxylic acid group; and the like.
The poly (phenylene) based polymer is not particularly limited as long as it includes a phenylene repeat unit. For example, it may include a homopolymer consisting of only phenylene repeat units, or may include a copolymer of a phenylene monomer with another monomer.
The poly (phenylene) based polymer can include any one or more of the following structures:
wherein R is 1 、R 2 、R 3 And R 4 Each independently is hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and
n is 1 to 20,000.
The poly (acetylene) based polymer is not particularly limited as long as each of the carbon and hydrogen atoms contains a repeating unit having a polyene (polyene) structure, for example, having (CH) x The repeating unit of the structure is sufficient. For example, it may include a homopolymer consisting only of repeating units having a polyene structure, or may include a copolymer of a polyene monomer with another monomer.
The poly (acetylene) based polymer may have a structure represented by the following chemical formula 4:
[ chemical formula 4 ]]
Wherein in chemical formula 4, n is 1 to 20,000.
In one embodiment of the present disclosure, the conductive polymer layer 20 may be formed by coating a conductive polymer solution onto the electrode current collector 10 and then drying it.
Referring to fig. 1, an electrode 1 for an electrochemical device according to one embodiment of the present disclosure includes an electrode active material layer 30 on an upper surface of a conductive polymer layer 20. The electrode active material layer 30 includes an electrode active material and a binder polymer.
In one embodiment of the present disclosure, the electrode active material layer may further include a conductive material in addition to the electrode active material and the binder polymer.
In one embodiment of the present disclosure, when the electrode 1 for an electrochemical device is a positive electrode, an electrode active material (i.e., a positive electrode active material) may include, for example, lithium transition metal oxide; lithium metal iron phosphate; lithium nickel manganese cobalt oxide; an oxide in which a part of the lithium nickel manganese cobalt oxide is substituted with another transition metal; two or more of them, but are not limited thereto. Specifically, the positive electrode active material may include, for example, lithium cobalt oxide (LiCoO) 2 ) Lithium nickel oxide (LiNiO) 2 ) Or a layered compound such as a compound substituted with one or more transition metals; such as Li 1+x Mn 2-x O 4 (wherein x is 0 to 0.33), liMnO 3 、LiMn 2 O 3 、LiMnO 2 Lithium manganese oxide of the same; lithium copper oxide (Li) 2 CuO 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Such as LiV 3 O 8 、LiV 3 O 4 、V 2 O 5 And Cu 2 V 2 O 7 Vanadium oxide of the same type; from chemical formula LiNi 1-x M x O 2 (wherein m= Co, mn, al, cu, fe, mg, B, or Ga, and x=0.01 to 0.3); from chemical formula LiMn 2-x M x O 2 (wherein m= Co, ni, fe, cr, zn, or Ta, and x=0.01 to 0.1) or Li 2 Mn 3 MO 8 (wherein m= Fe, co, ni, cu, or Zn); lithium metal phosphate LiMPO 4 (wherein m=fe, co, ni, or Mn); lithium nickel manganese cobalt oxide Li 1+x (Ni a Co b Mn c ) 1-x O 2 (wherein, x=0 to 0.03, a=0.3 to 0.95, b=0.01 to 0.35, c=0.01 to 0.5, a+b+c=1); oxide Li in which a part of lithium nickel manganese cobalt oxide is substituted with aluminum a [Ni b Co c Mn d Al e ] 1-f M1 f O 2 (wherein M1 is at least one selected from the group consisting of Zr, B, W, mg, ce, hf, ta, la, ti, sr, ba, F, P, and S, 0.8.ltoreq.a.ltoreq. 1.2,0.5.ltoreq.b.ltoreq. 0.99,0.ltoreq.c.ltoreq.0.5, 0 < d.ltoreq.0.5, 0.01.ltoreq.e.ltoreq.0.1, 0.ltoreq.f.ltoreq.0.1); oxide Li in which a part of lithium nickel manganese cobalt oxide is substituted with another transition metal 1+x (Ni a Co b Mn c M d ) 1-x O 2 (wherein x=0 to 0.03, a=0.3 to 0.95, b=0.01 to 0.35, c=0.01 to 0.5, d=0.001 to 0.03, a+b+c+d=1, m is any one selected from the group consisting of Fe, V, cr, ti, W, ta, mg, and Mo); a disulfide compound; fe (Fe) 2 (MoO 4 ) 3 And the like, but is not limited thereto.
In another embodiment of the present disclosure, when the electrode 1 for an electrochemical device is a negative electrode, the electrode active material (i.e., negative electrode active material) may typically include a carbon material, lithium metal, silicon-based material, tin, or the like, which can occlude and release lithium ions. The carbon material may include natural graphite, artificial graphite, low crystalline carbon, and high crystalline carbon. Typical examples of low crystalline carbon include soft carbon (soft carbon) and hard carbon (hard carbon), and typical examples of high crystalline carbon may include natural graphite, kish graphite (Kish graphite), pyrolytic carbon (pyrolitic carbon), mesophase pitch-based carbon fiber (mesophase pitch based carbon fiber), mesophase carbon microspheres (meso-carbon microbeads), mesophase pitch (Mesophase pitches), and high temperature calcined carbon such as petroleum or coal tar pitch-derived coke (petroleum or coal tar pitch derived cokes). Silicon-based materials may include silicon dioxide and the like.
The binder polymer may include polyvinylidene fluoride (polyvinylidene fluoride), polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetylene cellulose, polyvinyl chloride, polyvinylpyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene or polypropylene, acrylonitrile-butadiene rubber, styrene-butadiene rubber, acrylic rubber, or two or more thereof.
The conductive material is not particularly restricted so long as it has conductivity and does not cause chemical changes in the corresponding battery. The conductive material may include, for example, graphite such as natural graphite or artificial graphite; carbon blacks such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fibers and metal fibers; conductive tubes such as carbon nanotubes; a fluorocarbon; metal powders such as aluminum powder and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; a polyphenylene derivative; conductive materials such as graphene; and the like.
In one embodiment of the present disclosure, the weight ratio of the electrode active material to the binder polymer may be 90:10 to 98:2. 95:5 to 98:2. or 97:3 to 98:2.
In another embodiment of the present disclosure, when the electrode active material layer further includes a conductive material, the weight ratio of the electrode active material, the conductive material, and the binder polymer may be 90:5:5 to 98:1:1. or 95:2:3 to 98:1:1. or 97:1:2 to 98:1:1.
the electrode active material layer 30 may be prepared by a process in which the electrode active material, the binder polymer, and optionally, a slurry for forming the electrode active material layer, in which the conductive material is mixed with a dispersion medium, are coated onto the upper surface of the conductive polymer layer 20, dried, and then rolled.
An electrode for an electrochemical device according to one embodiment of the present disclosure is configured such that a conductive polymer layer is present on at least one surface of an electrode current collector, which may thus prevent direct short between the electrode current collectors when a short phenomenon occurs.
The potential of the electrode for the electrochemical device is similar to the potential at which the conductive polymer layer 20 interacts with the salt in the electrolyte, which may thus advantageously apply the conductive polymer layer 20 to the positive electrode. When the electrode for an electrochemical device is a positive electrode, it may protect the positive electrode from a hard short circuit, which may thus more advantageously ensure the safety of the electrochemical device.
In particular, the electrode for an electrochemical device according to one embodiment of the present disclosure has a conductive polymer layer on at least one surface of an electrode collector, compared to the case where the electrode active material layer is included together with the electrode active material layer, so that the conductive polymer layer may encapsulate the electrode collector, which may more effectively improve the safety of the electrode when a short circuit phenomenon occurs.
An electrode for an electrochemical device according to one embodiment of the present disclosure may be manufactured as an electrochemical device together with a separator.
An electrochemical device according to one embodiment of the present disclosure may be further improved in safety by including an electrode for an electrochemical device according to one embodiment of the present disclosure.
Electrochemical devices include all devices that undergo electrochemical reactions, and specific examples thereof include all kinds of primary and secondary batteries, fuel cells, solar cells, or capacitors (capacitors) such as supercapacitor devices, and the like.
In one embodiment of the present disclosure, the electrochemical device may be a lithium secondary battery including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery, and the like.
The separator is not particularly limited and is composed of only a porous polymer substrate, or may include a porous polymer substrate; and an organic-inorganic composite porous layer formed on at least one surface of the porous polymer substrate and including a plurality of inorganic particles and a binder polymer. The separator is interposed between the positive electrode and the negative electrode and serves to insulate between the positive electrode and the negative electrode.
The porous polymer substrate may be used without limitation as long as it is a porous polymer substrate generally used in the art. For example, a polyolefin-based porous polymer film (membrane) or a nonwoven fabric may be used as the porous polymer substrate, but is not particularly limited thereto.
The polyolefin-based porous polymer film may include a film (membrane) made from polyethylene such as high density polyethylene, linear low density polyethylene, or ultra high molecular weight polyethylene, polyolefin polymer such as polypropylene, polybutene, and polypentene, or two or more thereof.
In addition to the polyolefin-based nonwoven fabric, the nonwoven fabric may include, for example, nonwoven fabrics made from polyethylene terephthalate (pet), polybutylene terephthalate (pet), polyester (polyacetal), polyamide (polyamide), polycarbonate (polycarbonate), polyimide (polyimide), polyether ether ketone (polyethersulfone), polyphenylene ether (polyphenylene sulfide), polyethylene naphthalate (polyethylene naphthalate), or two or more thereof.
The structure of the nonwoven fabric may be a spunbond nonwoven fabric or a meltblown nonwoven fabric composed of long fibers.
The thickness of the porous polymer substrate is not particularly limited, but may be 3 μm to 50 μm, or 3 μm to 15 μm. The pore size and porosity present in the porous polymer substrate are also not particularly limited, but may be 0.01 μm to 50 μm and 10% to 95%, respectively.
In one embodiment of the present disclosure, the inorganic particles are not particularly limited as long as they are electrochemically stable. That is, the inorganic particles usable herein are not particularly limited as long as they are in the operating voltage range of the battery to be applied (for example, based on Li/Li + 0V to 5V) of (c) is not oxidized and/or reduced. The inorganic particles may include high dielectric constant inorganic particles having a dielectric constant of 5 or more or 10 or more, inorganic particles having lithium ion transfer ability, or two or more thereof. Having a dielectric constant of 5 or greaterThe inorganic particles may be BaTiO 3 、BaSO 4 、Pb(Zr,Ti)O 3 (PZT)、Pb 1-x La x Zr 1-y Ti y O 3 (PLZT, wherein 0 < x < 1,0 < y < 1), pb (Mg) 1/3 Nb 2/3 )O 3 -PbTiO 3 (PMN-PT), hafnium oxide (HfO) 2 )、SrTiO 3 、SnO 2 、CeO 2 、MgO、Mg(OH) 2 、NiO、CaO、ZnO、ZrO 2 、Y 2 O 3 、SiO 2 、Al 2 O 3 、γ-AlOOH、Al(OH) 3 、SiC、TiO 2 Or a mixture of two or more thereof, but is not limited thereto.
In one embodiment of the present disclosure, the size of the inorganic particles is not limited, but may have an average particle diameter in the range of 0.01 μm to 10 μm, or 0.05 μm to 1.0 μm in order to form an organic-inorganic composite porous layer having a uniform thickness and an appropriate porosity. At this time, the average particle diameter of the inorganic particles means a particle diameter (D50) at which the cumulative volume is 50% from the smaller particle size side, which is measured after classification with a usual particle size distribution meter, and calculated based on the measurement result. Such particle size distribution can be measured by laser diffraction analysis.
In one embodiment of the present disclosure, the binder polymer included in the separator may include polyvinylidene fluoride (PVdF), polyvinylidene fluoride-co-hexafluoropropylene (polyvinylidene fluoride-co-hexafluoroethylene), polyvinylidene fluoride-co-trichloroethylene (polyvinylidene fluoride-co-trichloroethylene), polyvinylidene fluoride-co-chlorotrifluoroethylene (polyvinylidene fluoride-co-chlorotrifluoroethylene), polymethyl methacrylate (polymethyl methacrylate), polyacrylonitrile (polyvinyl), polyvinylpyrrolidone (polyvinyl pyrrolidone), polyvinyl-co-vinyl acetate (polyvinyl acetate), polyethylene oxide (polyethylene oxide), cellulose acetate (cellulose acetate), cellulose acetate butyrate (cellulose acetate butyrate), cellulose acetate propionate (cellulose acetate propionate), cyanoethyl pullulan (cyanoethyl polysaccharide (cyanoethyl), polyvinyl alcohol (vinyl alcohol), cellulose acetate (26-vinyl acetate), cellulose acetate (sucrose), or a copolymer of two or more of them (polyethylene-vinyl acetate ), polyethylene-vinyl acetate (vinyl acetate), polyethylene-co-vinyl acetate (polyethylene), polyethylene-vinyl acetate (polyethylene-vinyl acetate), polyethylene-co-vinyl acetate (polyethylene), polyethylene-co-vinyl acetate (cellulose acetate propionate), and polyethylene-vinyl acetate (48).
In one embodiment of the present disclosure, the separator may include an inorganic particle to binder polymer content ratio of 20:80 to 99.9:0.1, 50:50 to 99.5:0.5, or 70:30 to 80:20. when the content ratio of the inorganic particles to the binder polymer is within the above range, the empty spaces formed between the inorganic particles can be sufficiently ensured while ensuring sufficient adhesive strength between the inorganic particles.
In one embodiment of the present disclosure, the organic-inorganic composite porous layers are bonded to each other by the binder polymer in a state that the inorganic particles are filled and contact each other, thereby forming interstitial volumes (interstitial volumes) between the inorganic particles. The interstitial volumes between the inorganic particles become empty spaces and may have a structure forming pores.
In one embodiment of the present disclosure, an electrochemical device includes an electrolyte, wherein the electrolyte may include an organic solvent and a lithium salt. In addition to this, an organic solid electrolyte, an inorganic solid electrolyte, or the like may be used as the electrolytic solution.
As the organic solvent, for example, aprotic organic solvents such as N-methyl-2-pyrrolidone, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, tetrahydroxyfuran (franc), 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl propionate, ethyl propionate can be used.
Lithium salts are materials that are rapidly soluble in organic solvents, and for example, can be used
LiCl、LiBr、LiI、LiClO 4 、LiBF 4 、LiB 10 Cl 10 、LiPF 6 、LiCF 3 SO 3 、LiCF 3 CO 2 、LiAsF 6 、LiSbF 6 、LiAlCl 4 、CH 3 SO 3 Li、CF 3 SO 3 Li、(CF 3 SO 2 ) 2 NLi, lithium chloroborane, lithium lower aliphatic carboxylate, lithium 4-phenylborate, imide, and the like.
In addition, for the purpose of improving charge/discharge characteristics, flame retardancy, and the like, for example, pyridine, triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine, N-ethyleneglycol dimethyl ether (glyme), hexaphosphoric triamide, nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N-substituted imidazolidinones, ethyleneglycol dialkyl ethers, ammonium salts, pyrrole, 2-methoxyethanol, aluminum trichloride, or the like may be added to the electrolyte. If necessary, a halogen-containing solvent such as carbon tetrachloride or trifluoroethylene may be further included so as to impart incombustibility, and carbon dioxide gas may be further included so as to improve high-temperature storage characteristics.
Examples of the organic solid electrolyte include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate polymers, poly-stirring lysines (agitation lysines), polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, and polymers including ion dissociating groups, and the like.
Examples of the inorganic solid electrolyte include nitrides, halides, and sulfates of lithium (Li), such as Li 3 N、LiI、Li 5 NI 2 、Li 3 N-LiI-LiOH、LiSiO 4 、LiSiO 4 -LiI-LiOH、Li 2 SiS 3 、Li 4 SiO 4 、Li 4 SiO 4 -LiI-LiOH、Li 3 PO 4 -Li 2 S-SiS 2 。
The injection of the electrolyte may be performed at an appropriate stage during the manufacturing process of the electrochemical device depending on the manufacturing process of the final product and the desired physical properties. That is, it may be applied before assembling the electrochemical device or at the final stage of assembling the electrochemical device.
As a process of applying the separator to the electrochemical device, in addition to winding (winding), which is a general process, lamination, stacking, and folding (folding) processes of the separator and the electrode may be performed.
The separator may be interposed between the positive electrode and the negative electrode of the electrochemical device, and may be interposed between adjacent cells or electrodes when a plurality of cells or electrodes are aggregated to form an electrode assembly. The electrode assembly may have various structures such as a simple stack type, a jelly-roll type, a stack-fold type, and a laminate-stack type.
The external appearance of the electrochemical device is not particularly limited, but may be cylindrical, prismatic, pouch (pouch) shaped, coin (coi) shaped, or the like using a can.
Hereinafter, embodiments will be described in detail with reference to examples in order to assist in understanding the present disclosure. Embodiments in accordance with the present disclosure may, however, be embodied in many different forms and the scope of the present invention should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be more fully explained to those skilled in the art.
Example 1
Synthesis of conductive Polymer and preparation of conductive Polymer solution
The conductive polymer was synthesized according to the following [ reaction scheme 1 ].
Reaction scheme 1
Specifically, 1g of 3-octylthiophene (Compound 1) (5.093 mmol,1 eq) as a monomer was added to a solution in which 2.48g of iron (III) chloride (15.3 mmol,3 eq) was dissolved in 70mL of chloroform, and the mixture was stirred at room temperature for 24 hours. The mixed solution was placed in a permeable membrane having an MWCO (molecular weight cut-off, molecular weight of cut off) of 5000 and then immersed in 200mL of acetonitrile solvent to selectively remove unreacted ferric (III) chloride and residual reactants. The residue precipitated inside the permeable membrane was washed with methanol and dried at room temperature. Thus, a polythiophene-based polymer having the same structure as that of Compound 2 and having a weight average molecular weight of 50,000g/mol was obtained as a conductive polymer.
The conductive polymer was dissolved in chloroform to prepare a 1 wt% conductive polymer solution, and filtered using a poly (tetrafluoroethylene) (PTFE) filter having pores of 1 μm.
Electrode fabrication
The conductive polymer solution was coated onto one surface of the body and the electrode tab of the aluminum current collector having a thickness of 20 μm and dried to form a conductive polymer layer having a thickness of 1 μm on one surface of the electrode current collector. The total thickness of the current collector coated with the conductive polymer was 21 μm.
LiCoO is added with 2 Carbon black, and poly (vinylidene fluoride) at 97.5:1:1.5 to an N-methyl-2-pyrrolidone (NMP) solution, and then mixed to prepare a slurry for forming an electrode active material layer. The solid content of the slurry for forming the electrode active material layer was 60 wt%.
The slurry for forming the electrode active material layer was coated onto an electrode current collector on which a conductive polymer layer was formed, dried and rolled (roll press) to manufacture an electrode having a total thickness of 50 μm.
Example 2
An electrode was manufactured in the same manner as in example 1, except that: the conductive polymer solution was coated so that the thickness of the conductive polymer layer formed on one surface of the current collector was 10 μm.
Example 3
An electrode was manufactured in the same manner as in example 1, except that: the conductive polymer synthesized according to the following [ reaction scheme 2] was used.
Reaction scheme 2
Specifically, 1.23g of 3-octylthiophene (6.26 mmol) and 1.41g of 3-decylthiophene (6.26 mmol) were added to a solution in which 6.09g of iron (III) chloride (37.6 mmol) was dissolved in 200ml of dichloromethane, and the mixture was stirred at room temperature for 24 hours. The mixed solution was placed in a permeable membrane having an MWCO (molecular weight cut-off, molecular weight of cut off) of 5000 and then immersed in 150mL of acetonitrile solvent to selectively remove unreacted ferric (III) chloride and residual reactants. The residue precipitated inside the permeable membrane was washed with methanol and dried at room temperature. Thus, a polythiophene-based polymer having the same structure as that of Compound 4 and having a weight average molecular weight of 33,000g/mol was obtained as a conductive polymer.
Comparative example 1
An electrode was manufactured in the same manner as in example 1, except that: the conductive polymer is not coated onto one surface of the electrode current collector.
Comparative example 2
LiCoO is added with 2 Carbon black, poly (vinylidene fluoride) and conductive polymer obtained in example 1 to 95.5:1:1.5:2 to an N-methyl-2-pyrrolidone (NMP) solution, and then mixing to prepare a slurry for forming an electrode active material layer. The solid content of the slurry for forming the electrode active material layer was 60 wt%.
The slurry for forming the electrode active material layer was coated on an aluminum current collector having a thickness of 20 μm, dried and rolled (roll press) to manufacture an electrode having a total thickness of 50 μm.
Comparative example 3
An electrode was manufactured in the same manner as in example 1, except that: poly (isothianthrene) is used as the conductive polymer.
Comparative example 4
An electrode was manufactured in the same manner as in example 1, except that: the conductive polymer synthesized according to the following [ reaction scheme 3] was used.
Reaction scheme 3
Specifically, 2.5g of 3-ethylthiophene (22.3 mmol) was added to a solution in which 10.84g of iron (III) chloride (66.85 mmol) was dissolved in 200ml of methylene chloride, and the mixture was stirred at room temperature for 24 hours. The mixed solution was placed in a permeable membrane having an MWCO (molecular weight cut-off, molecular weight of cut off) of 5000 and then immersed in 150mL of acetonitrile solvent to selectively remove unreacted ferric (III) chloride and residual reactants. The residue precipitated inside the permeable membrane was washed with methanol and dried at room temperature. Thus, a polythiophene-based polymer having a weight average molecular weight of 25,000g/mol was obtained as a conductive polymer.
Evaluation example
The adhesive strength between the conductive polymer layers and the electrode current collectors manufactured in examples 1 to 3 and comparative examples 1 to 4, the interfacial resistance between the conductive polymer layers and the electrode active material layers, the cycle efficiency, and the safety were evaluated, and are shown in table 1 below.
(1) Measurement of adhesion Strength between conductive Polymer layer and electrode Current collector
An electrode current collector having a conductive polymer layer formed thereon was attached and fixed to a glass plate using a double-sided adhesive tape, and the strength at which the electrode current collector portion was peeled off at an angle of 90 deg. at a speed of 20mm/min at 25 deg. was determined as the adhesive strength between the conductive polymer layer and the electrode current collector.
(2) Measurement of interfacial resistance between conductive polymer layer and electrode active material layer
Interface resistances between the conductive polymer layers and the electrode active material layers in the electrodes manufactured in examples 1 to 3 and comparative examples 3 to 4 were measured using a multi-probe tester.
In addition to this, the interface resistance between the electrode current collector and the electrode active material layer in the electrodes manufactured in comparative examples 1 and 2 was measured using a multi-probe tester.
(3) Evaluation of cycle efficiency
Artificial graphite, carbon black, and styrene butadiene rubber were blended at 95:3.5:1.5 to prepare a slurry for forming a negative electrode active material layer, which was coated on one surface of a copper thin film having a thickness of 8 μm, dried and rolled using a roll press to manufacture a negative electrode.
A polyethylene fabric having a thickness of 10 μm was interposed between the electrodes (positive electrodes) and negative electrodes manufactured in examples 1 to 3 and comparative examples 1 to 4, and pressed at 80 ℃ to prepare electrode assemblies.
Electrolyte (EC: PC: EP: pp=2:1:2.5:4.5, lipf 6 1.4M) (ion conductivity. Gtoreq.6.5 mS/cm) was injected into the prepared electrode assembly to manufacture an electrochemical device.
The electrochemical device manufactured above was subjected to constant current/constant voltage (CC/CV) charging at 0.7C rate up to 4.48V and 0.025C cut-off, and to Constant Current (CC) discharging at 0.2C rate up to 3.0V to evaluate cycle efficiency.
(4) Evaluation of safety
10 samples were prepared from each of the electrochemical devices manufactured above, and placed on a flat plate, on which an iron rod having a diameter of 15.8mm was placed, and then a weight of 9.1kg was freely dropped from a height of 61cm above. Impact tests were performed by this process to confirm the presence of combustion of the electrochemical device.
TABLE 1
As can be seen from table 1, it can be confirmed that since examples 1 to 3 include the conductive polymer layer, they have excellent safety.
In particular, it was confirmed that example 1 and example 3 had more excellent cycle efficiency than example 2 because the interfacial resistance between the conductive polymer layer and the electrode active material layer was 3.0ohm cm 2 Or smaller.
In addition to this, it was confirmed that example 1 had more excellent adhesive strength between the conductive polymer layer and the electrode current collector than example 3, and thus, was further improved in terms of safety.
On the other hand, since comparative example 1 and comparative example 2 did not include the conductive polymer layer, they did not ensure sufficient safety.
In particular, it was confirmed that although comparative example 3 and comparative example 4 included conductive polymer layers, they did not ensure sufficient adhesive strength between the conductive polymer layers and the current collector because the types of conductive polymers used were different.
[ reference numerals ]
1: electrode for electrochemical device
10: electrode current collector
20: conductive polymer layer
30: electrode active material layer
Claims (9)
1. An electrode for an electrochemical device, comprising:
an electrode current collector;
a conductive polymer layer on at least one surface of the electrode current collector; and
an electrode active material layer on an upper surface of the conductive polymer layer and including an electrode active material and a binder polymer,
wherein the conductive polymer layer comprises a poly (thiophene) (poly (thiophene)) based polymer represented by the following chemical formula 1:
[ chemical formula 1]
Wherein, in the chemical formula 1,
R 1 、R 2 、R 3 and R 4 Each independently is hydrogen or substituted or unsubstituted alkyl having 1 to 20 carbon atoms, R 1 And R is 2 Sum of carbon atoms of R 3 And R is 4 At least one of the total number of carbon atoms of 3 or more,
m and n are each independently integers from 0 to 20,000, and m+n > 0.
2. The electrode for an electrochemical device according to claim 1, wherein:
the adhesive strength between the conductive polymer layer and the electrode current collector is 200gf/20mm or more.
3. The electrode for an electrochemical device according to claim 1, wherein:
an interfacial resistance (interface resistance) between the conductive polymer layer and the electrode active material layer is 3.0ohm cm 2 Or smaller.
4. The electrode for an electrochemical device according to claim 1, wherein:
R 1 and R is 2 Sum of carbon atoms of R 3 And R is 4 At least one of the total number of carbon atoms of (2) is 5 or more.
5. The electrode for an electrochemical device according to claim 1, wherein:
the m or the n is 0.
6. The electrode for an electrochemical device according to claim 1, wherein:
the conductive polymer layer has a thickness of 0.1 μm to 8 μm.
7. The electrode for an electrochemical device according to claim 1, wherein:
the conductive polymer layer further comprises a poly (aniline) based polymer; poly (pyrrrole) based polymers; poly (phenylene) (poly (phenylene)) based polymers; poly (acetylene) (poly (acetylene)) based polymers; their derivatives; or two or more thereof.
8. The electrode for an electrochemical device according to claim 1, wherein:
the electrode for an electrochemical device is a positive electrode.
9. An electrochemical device includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode,
wherein the positive electrode or the negative electrode comprises the electrode for an electrochemical device according to any one of claims 1 to 8.
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| KR10-2022-0110984 | 2022-09-01 | ||
| KR1020220110984A KR20230037451A (en) | 2021-09-09 | 2022-09-01 | An electrode for electrochemical device and an electrochemical device comprising the same |
| PCT/KR2022/013560 WO2023038474A1 (en) | 2021-09-09 | 2022-09-08 | Electrode for electrochemical device and electrochemical device comprising same |
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