Negative electrode with carbon-based thin film, manufacturing method therefor, and lithium secondary battery comprising same
A negative electrode having a carbon-based thin film formed on at least one surface of a lithium metal layer, and a lithium secondary battery including the same. A carbon-based thin film formed on at least one surface of a lithium metal layer blocks side reactions caused by direct contact between the lithium metal layer and an electrolyte as well as increasing a specific surface area of a negative electrode, and thereby suppresses lithium dendrite formation, and by obtaining current density distribution uniformly, enhances cycle performance, reduces an overvoltage to improve electrochemical performance of a lithium secondary battery.
1. A negative electrode for a lithium secondary battery comprising:
a lithium metal layer;
a carbon-based thin film deposited on at least one surface of the lithium metal layer and having a thickness of 165 nm to 330 nm; and
an organosulfur protective layer on one surface of the carbon-based thin film not adjoining the lithium metal layer,
wherein the lithium metal layer has a thickness of 1 μm to 500 μm.
2. The negative electrode for a lithium secondary battery of claim 1 , wherein the lithium metal layer further includes a current collector on one surface not adjoining the carbon-based thin film.
3. The negative electrode for a lithium secondary battery of claim 1 , wherein the carbon-based thin film is formed with amorphous carbon.
4. The negative electrode for a lithium secondary battery of claim 1 , wherein the organosulfur protective layer includes an organosulfur compound, and the organosulfur compound includes a thiol group-containing monomer or polymer.
5. The negative electrode for a lithium secondary battery of claim 4 , wherein the organosulfur protective layer includes one or more types of compounds selected from the group consisting of 2,5-dimercapto-1,3,4-thiadiazole, bis(2-mercapto-ethyl)ether, N,N′-dimethyl-N,N′-dimercaptoethylene-diamine, N,N,N′,N′-tetramercapto-ethylenediamine, 2,4,6-trimercaptotriazole, N,N′-dimercapto-piperazine, 2,4-dimercaptopyrimidine, 1,2-ethanedithiol and bis(2-mercapto-ethyl)sulfide.
6. The negative electrode for a lithium secondary battery of claim 1 , wherein the organosulfur protective layer includes an electron conducting polymer.
7. The negative electrode for a lithium secondary battery of claim 6 , wherein the electron conducting polymer includes one or more types of compounds selected from the group consisting of polyaniline, poly(p-phenylene), polythiophene, poly(3-alkylthiophene), poly(3-alkoxythiophene), poly(crown ether thiophene), polypyrrole, poly(dialkyl-2,2′-bipyridine), polypyridine, polyalkylpyridine, poly(2,2′-bipyridine), poly(dialkyl-2,2′-bipyridine), polypyrimidine, polydihydrophenanthrene, polyquinoline, polyisoquinoline, poly(1,2,3-benzothiadiazole), poly(benzimidazole), poly(quinoxaline), poly(2,3-diarylquinoxaline), poly(1,5-naphthyridine), poly(1,3-cyclohexadiene), poly(anthraquinone), poly(Z-methylanthraquinone), poly(ferrocene) and poly(6,6′-biquinoline).
8. A lithium secondary battery comprising:
a positive electrode;
a negative electrode; and
an electrolyte,
wherein the negative electrode is the negative electrode of claim 1 .
9. The negative electrode for a lithium secondary battery of claim 1 , wherein an organosulfur compound is present in the organosulfur protective layer in an amount of 50% by weight to 100% by weight with respect to a total weight of the organosulfur protective layer.
10. The negative electrode for a lithium secondary battery of claim 3 , wherein the amorphous carbon comprises at least one of hard carbon, corks, mesocarbon microbead (MCMB) baked at 1500° C. or lower, or mesophase pitch-based carbon fiber (MPCF).