<2024> 리튬이차전지 Si-Anode 기술 현황 및 주요 업체 개발 동향
리튬이차전지의 음극활물질은 현재까지 주로 탄소재가 사용되고 있으며, 초기에는 비정질 탄소계를 많이 사용하였으나 지금은 천연흑연과 인조흑연을 주로 사용하고 있다. 최근에는 흑연 재료의 이론용량 한계를 극복하고 전기화학적 반응 전위 및 수명이 우수한 재료를 개발하기 위하여 Si계 음극소재를 중심으로 한 새로운 음극 재료들이 적극적으로 고려되고 있다. 전기자동차용 및 ESS용 중대형 배터리 시장에서 고용량 음극 소재의 필요성이 더욱 증가하면서 기존에 쓰이던 탄소계, 흑연계 음극재 중심에서 최근에는 특히 금속복합계인 실리콘(Si)계 음극재가 업계의 주목을 받고있으며, 이 소재를 확보려는 경쟁이 치열해지고 있다. 이와 관련하여 실리콘 음극재를 개발하고 양산하려는 신규 진입 업체들도 계속해서 증가하고 있다.
Si계 고용량 소재는 2020년 초에는 10~20개 업체에서만 주로 개발하고 있었으나, 현재는 60여개 이상 업체들이 개발 및 양산 준비를 하고 있다. Si계 소재는 향후 전기차의 주행거리 극복을 위한 고용량 전지개발 및 급속충전 요구사항을 만족하기 위해서는 필수적으로 개발되어야만 하는 소재이며, 전기차 OEM 및 배터리 업체들은 실리콘 음극재는 2035년까지 연평균 30%의 성장률이 예상된다. 전체 음극재 시장에서 실리콘 음극재의 비중은 2019년 1%에서 2030년 7%, 2035년 10%까지 확대할 전망이다.
탄소계, 흑연계 외에 리튬 이차전지 고용량 음극 소재로 Si-C composite, Si-alloy, SiOx 가 대표적이다. 그 중 SiOx 와 Si-alloy 는 가장 상품화에 근접되어 있으며, 일부 전지 메이커에서 전지에 적용하여 고용량 전지를 개발 중에 있으나, 아직까지 수명, 부피팽창(Swelling) 등의 문제가 있어 이를 개선하기 위한 노력을 진행 중이다. 실리콘(Si)계 음극 관련하여 최근 업계와 학계의 관련 기술 개발 발표가 잇따르고 있고, 음극 소재 업체들도 신규기술 개발에 집중하며 머지 않아 상용화가 기대되고 있다.
본 보고서는 최근 이슈가 되고 있는 xEV, ESS, IT용 리튬이차전지의 음극재 시장 뿐 아니라 고용량 전지개발을 위한 Si계 음극개발 동향 및 성능향상에 대한 기술적 보고서로, 특히, Si계 고용량 음극[Si-alloy, SiOx, Si-C composite]소재의 업체와 학계의 최신 개발 현황과 이를 적용한 전지의 상황 및 문제점 그리고 이를 개선할 수 있는 idea를 제공함으로 향후 고용량/고출력 전지 개발에 도움을 드리고자 한다.
본 보고서의 Striong Point
① 리튬이차전지 음극재의 전체적인 시장 M/S 및 기술 현황 (흑연계, 실리콘계 포함)
② 고용량 Si계 음극소재의 기술 이슈 및 핵심 요소 기술 정리
③ 배터리사의 최신 Si계 음극소재의 기술 개발 동향
④ 향후 Si계 음극소재의 응용 분야 및 상용화 전망
⑤ 글로벌 70여개의 실리콘 음극 업체 개발 동향 및 제품 소개
- Contents -
리포트 개요 ····································································································································· 10
Chapter Ⅰ. 리튬이차전지 개요
1.1 리튬이차전지 역사 ··················································································································· 12
1.2 리튬이차전지 종류 및 특징 ···································································································· 16
1.3. 리튬이차전지 원리 ·················································································································· 21
1.3.1 충전 및 방전반응
1.3.2 전압
1.3.3 전하와 이온의 이동
1.3.4 이론 용량
1.4. 리튬이차전지 구성요소 ········································································································· 35
1.4.1 양극활물질
1.4.2 음극활물질
1.4.3 분리막
1.4.4 전해질
1.5. 리튬이차전지 응용분야 ········································································································· 48
1.6. 음극재 기술 현황 및 개발 Trend ······················································································· 51
Chapter Ⅱ. 리튬이차전지 음극소재 종류 및 특징
2.1 리튬이차전지 음극소재 요구특성 및 종류 ········································································· 63
2.2 탄소계 음극소재 특성 ··········································································································· 65
2.2.1 흑연계 음극소재
2.2.2 비정질 탄소계 음극소재
2.2.3 탄소계 음극소재/전해질 계면 반응
2.3 금속계 음극소재 특성 ··········································································································· 87
2.3.1 리튬금속 음극소재
2.3.2 합금계 음극소재
2.4 화합물계 음극소재 특성 ······································································································ 106
2.4.1 산화물계 음극소재
2.4.2 질화물계 음극소재
Chapter Ⅲ. 고용량 리튬이차전지용 Si계 음극소재 기술개발 현황
3.1 고용량 리튬이차전지 개발 이력 및 방향 ········································································ 116
3.2 고용량 Si계 음극소재 기본 특성 ······················································································ 123
3.2.1 Si계 음극소재의 리튬 삽입/탈리 반응
3.2.2 Si계 음극소재의 문제점 및 열화 메커니즘
3.2.3 Si계 음극소재의 부피팽창 제어
3.3 합금계 음극재의 문제점 및 해결 방안 ·········································································· 137
3.3.1 대표적인 문제점
3.3.2 금속 복합계 음극재
3.3.3 금속-탄소 복합계 음극재
3.3 고용량 Si계 음극소재 기술개발 동향 ·············································································· 169
3.3.1 SiOx 음극소재
구조적 특성
전기화학적 특성
제조방법
Prelithiation 공정 적용
3.3.2 Si-C 복합체 음극소재
3.3.3 Si-M 합금 음극소재
3.3.4 Si계 음극재의 실제 적용 연구
전기화학적 거동 차이
Si 단독 전극 및 Si/흑연 혼합 전극
3.3.5 다양한 나노구조의 Si계 음극소재
Si nanostructure
Porous Si structure
Nano-Si/C structure
Nano-Si/metal or polymer structure
3.3.6 Si계 음극소재용 바인더
3.3.7 Si계 음극소재용 집전체
3.3.8 Si계 음극의 연구동향 종합 및 앞으로의 연구방향
3.3.9 Si계 음극소재 학계/업계 개발 사례
3.3.10 Si계 음극소재 주요 기술로드맵
Chapter Ⅳ. 고출력 Si계 음극소재 기술개발 현황
4.1 고출력 음극재의 개요 ········································································································ 236
4.2 고출력 급속충전용 음극소재 ························································································· 237
4.2.1 Intercalation소재
4.2.2 합금계 소재 / 전이 소재
4.2.3 nano 구조 마이크로 입자 (Nano-structured micro-sized particles)
4.2.4 Si-흑연 hybrid 소재 (SEAG)
4.2.5 Graphene-SiO2 소재 (Graphene Ball)
4.3 음극 관점에서 급속 충전 ···························································································· 248
4.3.1 음극재(활물질)의 영향 인자
4.3.2 전극의 영향 인자
4.3.3 주요 배터리 업체의 급속충전 기술 설계
4.4.4 종합 및 향후 전망
Chapter Ⅴ. LiB 음극재 시장 동향 및 전망
5.1 리튬이차전지 음극소재 시장 현황 ·················································································· 260
5.1.1 국가별 음극재 수요 현황
5.1.2 소재별 음극재 수요 현황
5.1.3 공급 업체별 시장 현황
5.1.4 LIB 업체별 수요 현황
SDI/LGES/SKon/Panasonic/CATL/ATL/BYD/Lishen/Guoxuan/AESC/CALB
5.2 리튬이차전지 음극소재 수급 전망··················································································· 306
5.2.1 음극재 생산캐파 전망
5.2.2 음극재 출하실적 현황 및 전망
5.2.3 음극재 수급 전망
5.3 리튬이차전지 음극소재 가격 전망··················································································· 310
5.3.1 음극재 가격 구조
NG/AG/Si계
5.3.2 음극재 가격 동향
NG/AG/Si계
5.3.3 흑연 종류별 가격 현황
5.3.4 Needle coke, Pitch 가격 현황
5.3.5 음극재 업체별 가격 전망
Chapter Ⅵ. 리튬이차전지 음극소재 생산업체 현황
6.1 리튬이차전지 음극소재 업체 요약 ················································································· 320
6.2 리튬이차전지 음극소재 생산업체 현황 ········································································· 324
흑연/카본계 중심 음극재 생산업체
1. BTR ···································································································································· 325
2. Shanshan ·························································································································· 330
3. Zichen ······························································································································· 334
4. Shinzoom(Changsha Xingcheng) ················································································ 337
5. Kaijin ································································································································· 341
6. XFH(XiangFengHua) ······································································································ 345
7. Hitachi Chemical(Resonac) ·························································································· 348
8. Mitsubishi Chemical ······································································································ 352
9. JFE Chemical ··················································································································· 355
10. 포스코퓨처엠 ················································································································· 358
11. 애경케미칼 ····················································································································· 362
실리콘계 중심 음극재 생산업체 (한국/아시아계)
12. 대주 전자재료 ··············································································································· 369
13. Shin-Etsu ························································································································ 375
14. MK전자 ··························································································································· 378
15. 일진전기 ························································································································· 382
16. EG ···································································································································· 385
17. 한솔케미칼 ····················································································································· 388
18. 이녹스에코켐 ·················································································································· 391
19. FIC 신소재 ······················································································································ 394
20. LPN ·································································································································· 398
21. Osaka Titan ···················································································································· 407
22. 포스코실리콘솔루션 ······································································································· 410
23. 티씨케이((TOKAI CARBON KOREA) ··········································································· 414
24. NM Tech(트루윈 인수) ·································································································· 416
25. KBG ·································································································································· 419
26. Neo Battery Materials ·································································································· 421
27. 한국메탈실리콘 ··············································································································· 427
28. 이엔플러스 ······················································································································· 430
29. 롯데에너지머티리얼즈 ···································································································· 432
30. 동진세미켐 ······················································································································· 434
31. SJ신소재 ··························································································································· 435
32. 아이엘사이언스 ··············································································································· 439
33. 에스머티리얼 ··················································································································· 442
34. ㈜HNS ······························································································································ 443
35. 와이파인텍 ······················································································································· 445
36. 하나 머티리얼즈 ·············································································································· 447
실리콘계 중심 음극재 생산업체 (중국계)
37. Haoxin Tech ····················································································································· 449
38. Longtime Tech ················································································································· 451
39. Gotion ······························································································································· 453
40. Shinghwa ·························································································································· 455
41. Tianmulake ······················································································································· 456
42. Chengdu Guibao ············································································································· 461
43. Jereh ·································································································································· 463
44. Huawei ······························································································································ 465
45. Xinan ································································································································· 469
46. Kingi ·································································································································· 471
실리콘계 중심 음극재 생산업체 (미주,유럽계)
47. Group14 (With SK 머티리얼즈) ···················································································· 474
48. NEXEON (With SKC) ······································································································· 478
49. Sila Nano Technologies ································································································· 483
50. Enovix ································································································································ 487
51. Enervate ···························································································································· 491
52. EO Cell ······························································································································· 495
53. Amprius Technologies ···································································································· 498
54. Nanotek' Instrument ······································································································ 503
55. One D ································································································································ 506
56. Nanograf ··························································································································· 510
57. LeydenJar ·························································································································· 512
58. ADVANO ···························································································································· 514
59. Targray ······························································································································· 517
60. 스토어닷(StoreDot) ·········································································································· 519
61. Trion Battery ··················································································································· 523
62. Black Diamond Structures ···························································································· 526
63. Nanospan ··························································································································· 527
Chapter Ⅶ. 참고 문헌