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Additives for Lithium Ion Batteries

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최종보고서

한양대학교 윤후영

연구제목: Preparation of high quality conductive material for Li-ion battery

실험 목표
본 연구에서는 기본적으로 섬유의 형성성이 좋은 PAN계 electrospun 섬유를 기반으로 하여 안정화, 탄화 한 후, 그 표면에 결정성의 열분해 탄소를 코팅한 후, 이를 다시 2400oC-280oC 열처리하여 섬유상의 전지 도전재를 제조하는 연구이다. 본 연구는 표면에 코팅된 pyrocarbon이 고온 흑연화 과정에서 PAN계 electrospun 탄화 섬유와는 다른 수축율을 지는 것에 의해 발생하는 응력을 이용하여, 보다 높은 흑연화 특성이 얻어짐으로써 보통 흑연화 과정만 거친 PAN계 electrospun에 비해 높은 전기전도성을 띌 것으로 기대한다.

실험 방법

중간 보고서에서 보고한대로 전기 방사한 PAN 섬유의 섬경을 800nm~1000nm로 맞추어 실험을 진행하려 했지만 생각보다 잘 되지 않고 시간이 부족한 관계로 방사가 잘되며 최대한 두꺼운 섬경을 가진 조건으로 실험을 마저 진행을 하였다. 방사의 조건은 tip의 inner diameter가 0.9mm, 길이가 18mm인 needle을 사용하였으며 tip-to-collector distance(TCD)는 15cm로 실험하였다. 용액은 PAN/DMF 12wt%의 농도로 하였으며 flow rate와 voltage는 각각 3ml/h 와 25kV로 하였다. Collector의 rotating speed는 100rpm, spinneret의 폭과 속도는 각각 100mm와 10mm/s로 설정하였다. 이렇게 제조된 섬유의 SEM 사진에서 100개를 무작위로 선택하여 측정한 결과 평균 395nm의 섬경을 얻었다. Bead는 존재하지 않은 깨끗한 섬유상의 결과물이 나왔다.
위의 방법으로 전기 방사하여 얻어진 알루미늄 호일 한 장에서의 샘플의 크기는 길이: 60cm 폭: 12~15cm 로 측정되었다. 이 한 장의 샘플을 4등분하여 자른 후 길이: 30cm 폭: 4.5cm로 자른 후 길이: 4.5cm 폭: 2~3cm 정도로 말아서 사용하였다. 석영 보트 위에 총 2개의 샘플이 얹혀지고 이를 길이가 60cm 인 전기로를 이용하여 안정화시켰다. 안정화 조건은 모두 200cc/min의 air 분위기에서 승온 속도 1oC/min으로 300oC까지 승온 후 300oC에서 1시간 유지하여 안정화 시켰으며 cooling 역시 air 분위기하에서 진행되었다.
Pyrocarbon coating은 길이가 30cm인 짧은 전기로에서만 할 수 밖에 없었기 때문에 안정화시킨 샘플 2개중 하나만 석영 보트 위에 올려서 코팅하였다. 200cc/min의 Ar 분위기에서 5oC/min의 승온 속도로 850oC까지 승온 후 850oC에서 Ar 가스를 끄면서 200cc/min의 CH4 가스로 교체하고 1, 2, 3시간 유지시켜주었다. 목표시간의 코팅 후 cooling은 다시 CH4 가스를 끄고 200cc/min의 Ar 가스로 교체하여 냉각하였다.
코팅이 완료된 샘플에 대해 일부를 잘라내어 흑연화를 시켰다. 흑연화는 먼저 진공 분위기에서 1300oC까지 승온 후, 1300oC에서 Ar 분위기로 만들어주고 2800oC까지 승온 후 2800oC에서 10분간 흑연화를 진행하였다.
위의 방법으로 얻어진 코팅된 샘플과 흑연화한 샘플을 원소분석, SEM, TEM, XRD, N2-BET의 방법으로 분석하였다.

Elemental analysis

O/C | 0.12 | 0.047 | 0.0082 | 0.022 | 0.40 | 0.23 | 0.34 | N/C | 0.36 | 0.12 | 0.13 | 0.12 | 0.41 | 0.35 | 0.37 | H/C | 0.064 | 0.0082 | 0.0036 | 0.0033 | 0.040 | 0.029 | 0.038 | Elemental analysis | Odiff | 7.82 % | 4.02 % | 0.72 % | 1.89 % | 21.74 % | 14.18 % | 19.6 % | | N | 23.17 % | 10.41 % | 11.16 % | 10.18 % | 21.96 % | 21.71 % | 21.15 % | | C | 64.83 % | 84.87 % | 87.8 % | 87.64 % | 54.14 % | 62.3 % | 57.06 % | | H | 4.18 % | 0.7 % | 0.32 % | 0.29 % | 2.16 % | 1.81 % | 2.19 % | Totalweight | 563.3 g | 584.6 g | 702.7 g | 609.5 g | 643.3 g | 693 g | 641.5 g | Sample | 850CH4C1h-1 | 850CH4C1h-2 | 850CH4C1h-3 | 850CH4C2h-1 | 850CH4C2h-2 | 850CH4C3h-1 | 850CH4C3h-2 |

Sample 850CH4C1h-1

Coating
Heating rate: 5oC/min in Ar atmosphere, up to 850oC
Coating: 1 hour in CH4 atmosphere at 850oC
Cooling: Ar atmosphere

| Weight | Yield | Remarks | As spun | 0.166 g | | | | Stabilization | 0.119 g | 71.69 % | | | Coating | 0.077 g | 46.39 % | NOVA 21번CH1H-1 TEM | 2/15 원소분석 1번 |

| | | | CH4 1h coating평균 섬경: 451nm |

Sample 850CH4C1h-2

Coating
Heating rate: 5oC/min in Ar atmosphere, up to 850oC
Coating: 1 hour in CH4 atmosphere at 850oC
Cooling: Ar atmosphere

Graphitization
10 minutes in Ar atmosphere at 2800oC

| Weight | Yield | Remarks | As spun | 0.270 g | | | | Stabilization | 0.192 g | 71.11 % | | | Coating | 0.126 g | 46.67 % | NOVA 22번CH1H-2 TEM | 2/10 원소분석 14번 |

| Weight | Yield | Remarks | Coated sample | 0.046 g | | | | Graphitization | 0.041 g | 89.13 % | NOVA 31번CH1HG-2 TEM | 2/20 원소분석 1번 |

| | CH4 1h coating | CH4 1h coating | | | CH4 1h coating평균 섬경: 311nm | CH4 1h coating + graphitization평균 섬경: 294nm | | | CH4 1h coating + graphitization | CH4 1h coating + graphitization |

Sample 850CH4C1h-3

Coating
Heating rate: 5oC/min in Ar atmosphere, up to 850oC
Coating: 1 hour in CH4 atmosphere at 850oC
Cooling: Ar atmosphere

| Weight | Yield | Remarks | As spun | 0.274 g | | | | Stabilization | 0.194 g | 70.80 % | | | Coating | 0.112 g | 40.88 % | NOVA 23번CH1H-3 TEM | 2/10 원소분석 13번XRD -3 |

| | | | CH4 1h coating평균 섬경: 347nm | |
Sample 850CH4C2h-1

Coating
Heating rate: 5oC/min in Ar atmosphere, up to 850oC
Coating: 2 hours in CH4 atmosphere at 850oC
Cooling: Ar atmosphere

Graphitization
10 minutes in Ar atmosphere at 2800oC

| Weight | Yield | Remarks | As spun | 0.160 g | | | | Stabilization | 0.117 g | 73.13 % | | | Coating | 0.081 g | 50.60 % | NOVA 24번CH2H-1 TEM | 2/10 원소분석 15번XRD -4 |

| Weight | Yield | Remarks | Coated sample | 0.040 g | | | | Graphitization | 0.037 g | 92.50 % | NOVA 32번CH2HG-1 TEM | 2/20 원소분석 2번XRD -9 |

| | CH4 2h coating | CH4 2h coating | | | CH4 2h coating평균 섬경: 414nm | CH4 2h coating + graphitization평균 섬경: 303nm | | | CH4 2h coating + graphitization | CH4 2h coating + graphitization |

Sample 850CH4C2h-2

Coating
Heating rate: 5oC/min in Ar atmosphere, up to 850oC
Coating: 2 hours in CH4 atmosphere at 850oC
Cooling: Ar atmosphere

Graphitization
10 minutes in Ar atmosphere at 2800oC

| Weight | Yield | Remarks | As spun | 0.285 g | | | | Stabilization | 0.192 g | 67.37 % | | | Coating | 0.115 g | 40.35 % | NOVA 25번CH2H-2 TEM | 2/15 원소분석 2번XRD -5 |

| Weight | Yield | Remarks | Coated sample | 0.030 g | | | | Graphitization | 0.025 g | 83.33 % | NOVA 33번CH2HG-2 TEM | 2/20 원소분석 3번XRD -10 |

| | CH4 2h coating | CH4 2h coating | | | CH4 2h coating평균 섬경: 319nm | CH4 2h coating + graphitization평균 섬경: 330nm | | | CH4 2h coating + graphitization | CH4 2h coating + graphitization |

Sample 850CH4C3h-1

Coating
Heating rate: 5oC/min in Ar atmosphere, up to 850oC
Coating: 3 hours in CH4 atmosphere at 850oC
Cooling: Ar atmosphere

| Weight | Yield | Remarks | As spun | 0.275 g | | | | Stabilization | 0.216 g | 78.54 % | | | Coating | 0.129 g | 46.90 % | NOVA 26번CH3H-1 TEM | 2/15 원소분석 3번XRD -6 |

| | | | CH4 3h coating평균 섬경: 516nm |

Sample 850CH4C3h-2

Coating
Heating rate: 5oC/min in Ar atmosphere, up to 850oC
Coating: 3 hours in CH4 atmosphere at 850oC
Cooling: Ar atmosphere

Graphitization
10 minutes in Ar atmosphere at 2800oC

| Weight | Yield | Remarks | As spun | 0.274 g | | | | Stabilization | 0.225 g | 82.12 % | | | Coating | 0.131 g | 47.81 % | NOVA 27번CH3H-2 TEM | 2/15 원소분석 4번XRD -7 |

| Weight | Yield | Remarks | Coated sample | 0.039 g | | | | Graphitization | 0.036 g | 92.31 % | NOVA 34번CH3HG-2 TEM | 2/20 원소분석 4번XRD- 11 |

| | CH4 3h coating | CH4 3h coating | | | CH4 3h coating 평균 섬경: 443nm | CH4 3h coating + graphitization평균 섬경: 410nm | | | CH4 3h coating + graphitization | CH4 3h coating + graphitization |

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