KR20230054296A - 리튬 이차전지용 양극 활물질 및 이의 제조방법 - Google Patents
리튬 이차전지용 양극 활물질 및 이의 제조방법 Download PDFInfo
- Publication number
- KR20230054296A KR20230054296A KR1020220132308A KR20220132308A KR20230054296A KR 20230054296 A KR20230054296 A KR 20230054296A KR 1020220132308 A KR1020220132308 A KR 1020220132308A KR 20220132308 A KR20220132308 A KR 20220132308A KR 20230054296 A KR20230054296 A KR 20230054296A
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- KR
- South Korea
- Prior art keywords
- active material
- transition metal
- metal oxide
- lithium
- lithium transition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 title claims description 31
- 239000006182 cathode active material Substances 0.000 claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims description 80
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims description 74
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 68
- 239000011164 primary particle Substances 0.000 claims description 58
- 239000011247 coating layer Substances 0.000 claims description 37
- 229910052759 nickel Inorganic materials 0.000 claims description 35
- 229910044991 metal oxide Inorganic materials 0.000 claims description 31
- 150000004706 metal oxides Chemical class 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 229910052723 transition metal Inorganic materials 0.000 claims description 23
- 150000003624 transition metals Chemical class 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 16
- 238000010304 firing Methods 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
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- 238000005245 sintering Methods 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
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- 239000011574 phosphorus Substances 0.000 claims 1
- -1 lithium transition metal Chemical class 0.000 description 26
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- 230000000052 comparative effect Effects 0.000 description 20
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
- 239000004698 Polyethylene Substances 0.000 description 3
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- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
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- 239000010442 halite Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
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- 239000004332 silver Substances 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
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- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 2
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 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
- 238000012827 research and development Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 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
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
도 2은 비교예 1의 양극 활물질을 나타낸 SEM 이미지이다.
도 3은 비교예 2의 양극 활물질을 나타낸 SEM 이미지이다.
실시예 1 | 비교예 1 | 비교예 2 | |
리튬 전이금속 산화물 내 1차 입자 평균 입경, D50 (㎛) | 2.0 | 2.0 | 2.0 |
금속 산화물 1차 입자 평균 입경, D50 (㎛) | 0.2 | - | - |
실시예 1 | 비교예 1 | 비교예 2 | |
저항 @SOC 5 (Ω) | 46.3 | 95.3 | 79.8 |
저항 @SOC 50 (Ω) | 10.9 | 16.1 | 14.7 |
저항 @SOC 95 (Ω) | 11.5 | 18.3 | 16.2 |
실시예 1 | 비교예 1 | 비교예 2 | |
용량 유지율 @30cycles(%) | 92.4 | 78.4 | 85.9 |
저항 증가율 @30cycles(%) | 31.0 | 87.5 | 79.1 |
Claims (11)
- 리튬을 제외한 전이금속 전체 몰수에 대하여 니켈을 60 몰% 이상 함유하는 리튬 전이금속 산화물; 및 상기 리튬 전이금속 산화물의 표면에 위치하며, 금속 산화물을 포함하는 코팅층;을 포함하고,
상기 리튬 전이금속 산화물은 평균 입경(D50)이 0.7 내지 3㎛인 1차 입자를 포함하는 단입자이고,
상기 금속 산화물은 평균 입경(D50)이 0.5㎛ 이하인 1차 입자로, Ni, Co, Mn, Al, B, Ti, Ta, W 및 Nb로 이루어진 군에서 선택된 1종 이상의 금속 원소를 포함하는 것인, 양극 활물질.
- 청구항 1에 있어서,
상기 코팅층의 두께는 0.02 내지 2.4㎛인 양극 활물질.
- 청구항 1에 있어서,
상기 리튬 전이금속 산화물 및 코팅층의 부피비는 50 : 50 내지 95 : 5인 양극 활물질.
- 청구항 1에 있어서,
상기 리튬 전이금속 산화물은 평균 입경(D50)이 1 내지 10㎛인 단입자인 양극 활물질.
- 청구항 1에 있어서,
상기 단입자 1개는 2 내지 30개의 1차 입자로 이루어진 양극 활물질.
- 청구항 1에 있어서,
상기 리튬 전이금속 산화물은 하기 화학식 1로 표시되는 것인 양극 활물질:
[화학식 1]
Li1+aNixCoyMnzM1 wO2
상기 화학식 1에서,
M1은 Al, Mg, V, Ti 및 Zr으로 이루어진 군에서 선택되는 적어도 어느 하나이고,
0≤a≤0.5, 0.6≤x<1, 0<y≤0.4, 0<z≤0.4, 0<w≤0.04, x+y+z+w=1임.
- (S1) 전이금속 전체 몰수에 대하여 니켈을 60 몰% 이상 함유하는 전이금속 수산화물을 준비하는 단계;
(S2) 상기 전이금속 수산화물과 리튬 원료물질을 혼합하고 800 내지 890℃의 온도에서 소성하여, 단입자의 리튬 전이금속 산화물을 제조하는 단계;
(S3) 상기 리튬 전이금속 산화물을 상기 소성 온도보다 30 내지 50℃ 높은 온도에서 열처리하는 단계; 및
(S4) 상기 열처리된 리튬 전이금속 산화물과, Ni, Co, Mn, Al, B, Ti, Ta, W 및 Nb로 이루어진 군에서 선택된 1종 이상의 금속 원소를 포함하는 코팅 원료 물질을 혼합하고 열처리하는 단계;를 포함하는 양극 활물질의 제조방법.
- 청구항 7에 있어서,
상기 단계 (S4)에서 열처리는 600 내지 700℃ 온도에서 수행되는 양극 활물질의 제조방법.
- 청구항 7에 있어서,
상기 소성은 산소 또는 공기 분위기 하에서 수행되는 양극 활물질의 제조방법.
- 청구항 1 내지 6 중 어느 한 항의 양극 활물질을 포함하는 리튬 이차전지용 양극.
- 청구항 10의 리튬 이차전지용 양극을 포함하는 리튬 이차전지.
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Cited By (13)
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WO2024237715A1 (ko) * | 2023-05-18 | 2024-11-21 | 주식회사 엘지화학 | 양극재, 이를 포함하는 양극 및 리튬 이차 전지 |
WO2024237714A1 (ko) * | 2023-05-18 | 2024-11-21 | 주식회사 엘지화학 | 양극재, 이를 포함하는 양극 및 리튬 이차 전지 |
WO2024237718A1 (ko) * | 2023-05-18 | 2024-11-21 | 주식회사 엘지화학 | 양극재, 이를 포함하는 양극 및 리튬 이차 전지 |
KR20240166876A (ko) * | 2023-05-18 | 2024-11-26 | 주식회사 엘지화학 | 양극재, 이를 포함하는 양극 및 리튬 이차 전지 |
KR20240166935A (ko) * | 2023-05-18 | 2024-11-26 | 주식회사 엘지화학 | 양극재, 이를 포함하는 양극 및 리튬 이차 전지 |
WO2024248543A1 (ko) * | 2023-06-02 | 2024-12-05 | 주식회사 엘지화학 | 양극 활물질, 및 이를 포함하는 양극 및 리튬 이차전지 |
WO2024248544A1 (ko) * | 2023-06-02 | 2024-12-05 | 주식회사 엘지화학 | 양극 활물질, 및 이를 포함하는 양극 및 리튬 이차전지 |
WO2025005661A1 (ko) * | 2023-06-27 | 2025-01-02 | (주)포스코퓨처엠 | 리튬 이차 전지용 양극 활물질의 제조방법 및 이를 이용하여 제조된 양극 활물질을 포함하는 리튬 이차 전지 |
WO2025005660A1 (ko) * | 2023-06-27 | 2025-01-02 | (주)포스코퓨처엠 | 리튬 이차 전지용 양극 활물질의 제조방법 및 이를 이용하여 제조된 양극 활물질을 포함하는 리튬 이차 전지 |
WO2025037948A1 (ko) * | 2023-08-17 | 2025-02-20 | 주식회사 엘지화학 | 양극 활물질의 제조 방법 |
WO2025071087A1 (ko) * | 2023-09-25 | 2025-04-03 | (주)포스코퓨처엠 | 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지 |
WO2025089934A1 (ko) * | 2023-10-26 | 2025-05-01 | 포스코홀딩스 주식회사 | 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지 |
WO2025095715A1 (ko) * | 2023-11-03 | 2025-05-08 | 주식회사 엘지화학 | 양극 활물질, 이의 제조 방법, 및 이를 포함하는 양극 및 리튬 이차전지 |
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WO2024237715A1 (ko) * | 2023-05-18 | 2024-11-21 | 주식회사 엘지화학 | 양극재, 이를 포함하는 양극 및 리튬 이차 전지 |
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WO2024237718A1 (ko) * | 2023-05-18 | 2024-11-21 | 주식회사 엘지화학 | 양극재, 이를 포함하는 양극 및 리튬 이차 전지 |
KR20240166876A (ko) * | 2023-05-18 | 2024-11-26 | 주식회사 엘지화학 | 양극재, 이를 포함하는 양극 및 리튬 이차 전지 |
KR20240166875A (ko) * | 2023-05-18 | 2024-11-26 | 주식회사 엘지화학 | 양극재, 이를 포함하는 양극 및 리튬 이차 전지 |
KR20240166873A (ko) * | 2023-05-18 | 2024-11-26 | 주식회사 엘지화학 | 양극재, 이를 포함하는 양극 및 리튬 이차 전지 |
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WO2024248543A1 (ko) * | 2023-06-02 | 2024-12-05 | 주식회사 엘지화학 | 양극 활물질, 및 이를 포함하는 양극 및 리튬 이차전지 |
WO2024248544A1 (ko) * | 2023-06-02 | 2024-12-05 | 주식회사 엘지화학 | 양극 활물질, 및 이를 포함하는 양극 및 리튬 이차전지 |
WO2025005661A1 (ko) * | 2023-06-27 | 2025-01-02 | (주)포스코퓨처엠 | 리튬 이차 전지용 양극 활물질의 제조방법 및 이를 이용하여 제조된 양극 활물질을 포함하는 리튬 이차 전지 |
WO2025005660A1 (ko) * | 2023-06-27 | 2025-01-02 | (주)포스코퓨처엠 | 리튬 이차 전지용 양극 활물질의 제조방법 및 이를 이용하여 제조된 양극 활물질을 포함하는 리튬 이차 전지 |
WO2025037948A1 (ko) * | 2023-08-17 | 2025-02-20 | 주식회사 엘지화학 | 양극 활물질의 제조 방법 |
WO2025071087A1 (ko) * | 2023-09-25 | 2025-04-03 | (주)포스코퓨처엠 | 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지 |
WO2025089934A1 (ko) * | 2023-10-26 | 2025-05-01 | 포스코홀딩스 주식회사 | 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지 |
WO2025095715A1 (ko) * | 2023-11-03 | 2025-05-08 | 주식회사 엘지화학 | 양극 활물질, 이의 제조 방법, 및 이를 포함하는 양극 및 리튬 이차전지 |
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JP7608013B2 (ja) | 2025-01-06 |
WO2023063778A1 (ko) | 2023-04-20 |
CA3217171A1 (en) | 2023-04-20 |
US20240186504A1 (en) | 2024-06-06 |
CN117178386A (zh) | 2023-12-05 |
JP2024512946A (ja) | 2024-03-21 |
EP4303959A4 (en) | 2024-10-16 |
EP4303959A1 (en) | 2024-01-10 |
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