Carbon Letters Vol. 9, No. 1 March 2008 pp. 35-46 Patent Trends of Carbonaceous Materials for Hydrogen Storage (III): Major Applicants & Technology Flow-chart Soo-Jin Park 1,, Byung-Joo Kim 2 and Young-Seak Lee 3 1 Dept. of Chemistry, Inha Univ., 253 Nam-gu, Incheon 402-751, Korea 2 Dept. of Green Chemistry & Environmental Biotechnology, Univ. of Science and Technology, P.O. Box 107, Yuseong, Daejeon 305-600, Korea 3 Dept. of Fine Chemical Engineering and Chemistry, Chungnam National Univ., 220 Kung-dong, Yuseong, Daejeon 305-764, Korea e-mail: sjpark@inha.ac.kr (Received July 9, 2007; Accepted February 25, 2008) lvp rs, rq, pnp r lvop tq Kyoto Protocol eqp rrp Zero Emission p en l. l ro ~lvop o k l v l ep n vtlp, np n p lvop pl ps l lv v p n p [1-5]. lv prp p r llv ~rlvp, o p l lvf l v rp }p pe p. p l e p p p, p v p l r } r l k. lv lrl p ˆ v k l rr n rqp n sp l rrp ~ p p v p. l m 2030l rp q n t ˆn, n p 1}500l p l v pn eqp rq, n, r n p eq 1s j o p r [15-10]. pl rp lv l v pp, p n lv, tn q rol~p tep lv p q l ~rp v l v tl p. pp n 2003 8o l ep oq p el, r t p lv l v p. np n p lv rs rq pn Žl l p l l ll l lvp ~ r p o l v tl p. q lv erp n o l p rs, kr rq, p pn p lk. p n p rs sp rs el p k e p rs q r rp p r p oql lp pn, ˆk, v k qllv pn p l p. v p rs q n, tˆn, np pn o lvp kr rq np e lk p [11]. qv rqp k~rq, ~ rq, rq p p. pt k~rqp k eˆ p np n n t m o v p q r k p. ~rqp n 400 k rp kp p kqp p n, kp l p o p p. q p p m p r p p pp p kp rq p p, rq 100% pnv k p mrp p l, rp nl lnp p. pl p k ml n m m rp n p lrp rq ƒvp v rq qp np lp, ˆqm p q pn p n p sp s l p rq q l p l v p ˆp. k p lv v r, r r Ž sp q r pp, pl p r ˆr ml l n rrp kp ˆ p. p r l n 2015 4000l pp eqp } 5op tp p. k p o} p r o lv p l ll ~r l p o p re n [11]. p k m ˆ q pn r q: (1) rr ˆ q pn rq: (2) rr l pp (3) tn op tn rq
36 Soo-Jin Park et al. / Carbon Letters Vol. 9, No. 1 (2008) 35-46 n ˆqp l ~r q lvp e k p Žk k p p l rp l p el vrqp ml p r lp vt l, l l o p Ž el q l l l. px l k l r rr p tn op tn ˆqp m. l rqn ˆqm p o 332p l p q mp, 2007 4o v ˆq m. r p erp l op tp 2004 12ovp p m. l v rqn ˆq ˆ (activated carbons, ACs activated carbon fibers, ACFs), l (graphites pk), ˆ (carbon nanotubes, CNTs), ˆo (carbon nanofibers, CNFs graphite nanofibers, GNFs), (fullerene), n ˆp 7 k mp, nk ˆq r vq~, m ˆ, ˆ l vp p p k, p ˆq t 1s 1s p ˆ p p, ˆ k 6 kl v k ˆq, n ˆp ˆq l ˆqp ~rp lp l p. px rqn ˆqm l r rp o Table 1. Sony Corpp - ( o t: ~ 2006) l p o 2000-7 - 1 8 2001-3 4-7 2002 1 7 1 1 10 2003 1 1 - - 2 2004 1 - - - 1 2005 - - - - 0 3 18 5 2 28 q p Sony Corp, Nissan Motor Corp, Toyota Motor Corpp 3 tn opp r l opp m p tn np l, p p m [12-18]. 3.1.1. Sony Corpp 2006v o t 2007 4ov ( ) Sony Corpp, 2000 2004 v, p, ol o mp, pl vtrp o p ˆ. r rp 2000 2002vp 3 r~ o 28 tp p 25p ol, pl 2000 2002l, l 2001l p q p l (Table 1). Table 2l ˆ q l, Sony Corpp 2000 2004v ˆ, ˆo,, n ˆ kl t o mp, ˆ o, ˆo n l op vtl p pp pl l l p s ˆq pn rqp e p l., ˆ l p sp q pn kl op r plvv kp p l., Sony Corpp p t ˆql r / r }l m ˆrp vp p ˆ ql p p, nl rnk, Table 2. Sony Corpp q- ( o t: ~ 2006) l ˆ l CNT CNF n ˆ 2000 - - 2-1 6-9 2001 - - 1 5-1 1 8 2002 - - 3 3-3 3 12 2003 - - 1 - - 1-2 2004 - - 1 1 - - 2 2005 - - - - - - - 0 0 0 8 9 1 11 4 33
Patent Trends of Carbonaceous Materials for Hydrogen Storage (III): Major Applicants & Technology Flow-chart 37 Table 3. Sony Corpp Š ˆ rq, pp EP 1,219,567 () n v () n v US 7,014,952 ˆq(, ˆ) ˆo pd v k ol 400 o C, 1k p l edš l ˆq r JP 2001-348216 } qeˆ p k ˆ JP 2002-128501 l qeˆ ~, r~l vp p o p p. ˆql r / r } l}, rqž s, k }, Ž p plp, ~ ~l ol (Table 3). Sony Corpp p p Sony Corp q~ r rq ˆo ˆ p rqq pn l llp p, p r t Sony Corp q~rp s ˆq rq yp pn eˆ rl p q yp l ˆ p m. 3.1.2. Nissan Motor Co Ltdp Table 4 Nissan Motor Co Ltdp p. 2006v o t 2007 4ov ( ) Nissan Motor Co Ltdp, Sony Corpm v pl vtrp o p ˆ. 2000 2002 2005v pl op plr, 2002 2004v 3 r JP 2002-151094 ˆq (, ˆ, ˆ o) pn lrv JP 2002-228099 kn pn q q JP ˆo p ˆ o, 200- l rqvp ˆ US 7,008,725 JP 2003-054901 1400 o C, 1kl o ˆq 100-800 o C, d o l lp p ˆ US 7,037,622 l 50k pl JP 1,426,33, ˆ ˆ qeˆ o ˆo 400-800 US 7,014,951 o C, 10.1 Pal EP 2003-210976 l} 102004000 KR ˆq pn rq JP 2003-210977 l} 4485 ol ˆql rqž Š p pn l ˆs~ JP 2001-302223 JP 2003-231099 s rs pp p ˆq (ˆ, ˆ JP 2001-316104 o, l)p r p eˆ JP 2003-238133 oq oqp p ˆ JP 2001-328804 kdž 100 p p o ˆq k (Az(1-x)BzxAlHy) ˆ JP 2004-026623 q (ˆ, ˆo) JP 2001-328805 n } ˆq ˆq ( l, ˆ, ˆ JP 2004-122036 o) kvl JP 2004-168581 ˆo 2004-2004- 230274 ˆ } l} ~ 19t 16p olp, 2003l 7p ol t p q p ˆ. tn l q, Nissan Motor Co Ltd 2000 2005vp ˆ, l, ˆo, ˆ, n kl o mp, l ˆ kl o p vt p ˆ Table 4. Nissan Motor Co Ltdp - ( o t: ~ 2006) l p o 2000-2 - - 2 2001 - - - - 0 2002-4 - - 4 2003-7 - - 7 2004-5 - - 5 2005-1 - - 1 0 19 0 0 19
38 Soo-Jin Park et al. / Carbon Letters Vol. 9, No. 1 (2008) 35-46 Table 5. Nissan Motor Co Ltdp q- ( o t: ~ 2006) ˆ l CNT CNF n ˆ 2000 - - 2 1 - - - 3 2001 - - - - - - - 0 2002-2 - - - 2-4 2003 1 3 3 - - - - 7 2004-4 - - - 1-5 2005-1 - - - - - 1 1 10 5 1 0 3 0 20 Table 6. Nissan Motor Co Ltdp () n v () n v ˆ d r q l JP 2001-205085 JP 2005-021876 l r mr rq~ JP 2001-288626 n ƒp q l ˆ / ˆ r r ~ o (oj, q, pm k JP 2005-021750,, v)l m m k lp ˆ v rl 1-40 nmp s l pv~ JP 2005-041742 JP 2003-321215 pp 1-60 µmp rqp JP 2003-321216 rp 400 m 2 /gp p 5nm p p p nrp 0.3 cm 3 /gp l rq~ JP 2005-046702 JP 2004-052814 ˆq pn rqq JP 2005-125304 JP 2004-211718 o ˆqm ˆq a > b, 20 X 20 + 80(b/a) s q~ (a:ˆp q, b:oˆp q, x:oˆp o) v p r l l oq q p l p oq qp p r r l oq p r p oq p v l s~ v rq~ JP 2006-043693 l p o p p r r rp l l k p l pl l o oqp p JP 2004-268022 0.8-1.2 nm r l JP 2006-015291 r r l JP 2004-292187 rp l ˆ JP 2006-026567 JP 2004-290793 l ˆ JP 2006-035105 JP 2004-313906 q n} ˆ l oq l v 3D 0 /R 0 10 s D 0 : m Š R 0 : p 0p ˆq ( ˆ, o~, l v)l p o rq~ (Table 5). r~ 20 t 10 5p l ˆ kl o p lk, k l tp r vrp plp p Ž. 2006v o 2007 4ov Nissan Motor
Patent Trends of Carbonaceous Materials for Hydrogen Storage (III): Major Applicants & Technology Flow-chart 39 Co Ltdp op tp l, l r ˆq ˆm ˆo kl ep mp, r rp l k ep p p Ž. Nissan Motor Co Ltdp tnp t ˆql r }m ˆrp vp p ˆql p p, nl ~ r~l vl o p m. ˆp n, ˆ q~ p rnl ˆp s ˆ l o p p op v l, lp n, lp p qeˆ rvl vp p ol, ˆ o o l m m klp m, ~ ˆq m ~ ol (Table 6). 3.1.2. Toyota Motor Corpp Table 7p Toyota Motor Corpp ˆ p, 2006v o t 2007 4ov ( ) Toyota Motor Corpp, p l 16p olp, 2002l 7p ol o p q p ˆ. op 1996l plr tn op t rqn ˆq l rp p mp, t p plv v kkp, 2003 2000 2004l o p p. Toyota Motor Corpp erp n kl m o p mp, 2002l q p ˆ. l ˆ, ˆ ˆol o p plrp nl l p tp, v q~ l ˆ kl op ll p l. 2006v o 2007 4ov Toyota Motor Corpp op tp l ˆq Table 7. Toyota Motor Corpp - ( o t: ~ 2006) l p o 1996-1 - - 1 1997 - - - - 0 1998 - - - - 0 1999 - - - - 0 2000-3 - - 3 2001 - - - - 0 2002-7 - - 7 2003-3 - - 3 2004-2 - - 2 2005 - - - - 0 0 16 0 0 16 r v q~l trp nl ep p p l. Toyota Motor Corpp ˆqm p ~, ˆql v p ˆ v rq~, ˆrp vp p ˆq, ˆql v p l qeˆ l o p plp, q lp Table 9l ˆ l. q p l p o sl q p nl m ˆ l p s ˆqp ˆ ˆ op p l, kp r p ˆv l k [12-18]. Table 8. Toyota Motor Corpp q- ( o t: ~ 2006) l ˆ l CNT CNF n ˆ 1996 - - - - - 1-1 1997 - - - - - - - 0 1998 - - - - - - - 0 1999 - - - - - - - 0 2000 1 - - 1-1 - 3 2002 - - - 1-6 - 7 2003 - - 1 - - 2-3 2004 - - 1 - - 1-2 2005 - - - - - - - 0 1 0 2 2 0 11 0 16
40 Soo-Jin Park et al. / Carbon Letters Vol. 9, No. 1 (2008) 35-46 Table 9. Nissan Motor Co Ltdp () n v () n v p p ˆq (, ˆ, ˆ) JP 2004-059409 k l rq JP 1998-072201 3.2.1. ˆp v ( ) t ˆ l m. 1986 Syracuse Universityl p ˆ-rp ~ rqq l rn p eqp 1989 Syracuse Universityp k ˆ, 1992 Martin Marietta Energy Systems incp l- s~, 1999 Japan Steel Works Ltdp lrvv- ˆ, Asahi Glass Co Ltd rq - ˆ, 2000 Toyota Motor Corpp p ˆp p p p (Fig. 1). ˆp pn n ˆp s~l ˆp r r } p l rq p v p p p o pp p l. l ˆ rsl pl ovl 2002 Mitsubishi Gas Chem Co Incp m t pn, 2003 Nissan Motor Co l, Žl / Ž ˆq (ˆ, ˆ o, ˆ ) vp 0.5-1000 nmp p ˆ ˆq ( ˆ, ˆ, ˆ JP 2001-220101 q (ˆ, ˆo, JP 2004-116565 o)m r 1- ˆ)l qe 50ìmp p r rq JP 2001-288624 l Li K v ˆo JP 2004-131853 voq o ˆo ˆoqp ovl v ˆ l p oql p p vp ˆq JP 2002-126506 p p rq~ JP 2004-237232 (ˆ, ˆo,, l)l l l rq pvl 2 pq ˆ (, l, ˆ) 1 pqm ˆq ( ˆ, ˆ, l ) JP 2003-210974 JP 2004-261739 1 pq pl p pq p l rq p r q~ JP 2004-028236 JP 2004-026604 JP 2004-051430 rqr [ p ˆq ( ˆ, ˆ, ˆ o, ˆ, ), r, r, k r kp rq q p (Ag, Mo Ru, Cu, Ni, Col ˆ 1s pp Pd ) p ˆq (ˆ, ˆo, ˆ, ) rq 8s }pl ˆ 1s pp p v ˆq ( ˆ, ˆ, ˆo, ˆ, ) JP 2005-137970 k (ˆ)- ( ˆ )sp rq~ JP 2005-324971 vp 2-10 nmp ˆ JP 2006-035174 ˆq (ˆ, ˆo,, l)p p vp ˆŽ r qž l l rq Ltdp o p oom m k lp pn, 2004 lop p pn ˆ o ol. ˆ ( ˆo )p s n l m r rp q l, t, p q ˆ sq, rp 500 ~ 2000 m 2 /g, 0.2 ~ 1.5 cm 3 /g rp. prp ˆ q~p pn l rqp e n ˆp p p p l p rqp p. p o sp rpp p p e l rqp l ep l p p. p l l p p v pp, l p r rl ˆp p p rp/ ˆ ~p rl l p ˆp l
Patent Trends of Carbonaceous Materials for Hydrogen Storage (III): Major Applicants & Technology Flow-chart Fig. 1. 으로 예측된다. 3.2.2. 흑연의 기술 흐름도 41 활성탄의 기술 흐름도 최근까지 공개 (미국특허는 등록)된 특허 중 흑연 기술과 관 련된 특허를 분류하여 분석하였다. 1976년 미국의 The United States of America as represented by the Administrator of the
42 Soo-Jin Park et al. / Carbon Letters Vol. 9, No. 1 (2008) 35-46 흑연의 기술 흐름도 수소저장합금을 충전하여 전극으로 사용하는 기술, 1999년 National Aeronautics and Space Administration의 자기장을 이 용하여 흑연에 수소를 저장하는 방법에 관한 출원을 시작으로 Electrion Inc의 흑연을 포함하는 수소저장체를 자동차에 적용 하는 기술, Tokyo Gas Co Ltd의 흑연을 팽창시키는 기술, 2001 1992년 Sanyo Electric Co Ltd의 흑연의 삼차원적 메트리스에 Fig. 2.
Patent Trends of Carbonaceous Materials for Hydrogen Storage (III): Major Applicants & Technology Flow-chart 43 탄소나노튜브의 기술 흐름도 년 Nippon Telegr & Teleph Corp <NTT>의 흑연-Ti 복합체, 초기에는 수소저장체로 흑연물질 자체 또는 적용분야에 출원 이 이루어지지만 점차적으로 흑연을 기계적으로 처리하는 기 2003년 Nissan Motor Co Ltd의 흑연층간의 거리를 확장하는 기술까지 지속적인 발전이 이루어져 왔다 (Fig. 2). 기술발전 술, 흑연 층간의 거리를 확장하거나 내부에 수소를 저장할 수 Fig. 3.
44 Soo-Jin Park et al. / Carbon Letters Vol. 9, No. 1 (2008) 35-46 탄소나노섬유의 기술 흐름도 있는 공간부를 형성하는 기술 및 흑연 층간에 삽입되는 물질 판상의 흑연이 겹겹의 층상으로 이루어진 것으로 각층은 강한 van der Waals forces로 연결되어 있다. 하지만 약간의 화학적 에 출원이 주를 이루고 있다. 흑연은 활성탄과 더불어 전통적인 소재이다. 흑연의 구조는 처리나 열처리를 통해 층상의 간격이 제어가 가능하여, 임의 Fig. 4.
Patent Trends of Carbonaceous Materials for Hydrogen Storage (III): Major Applicants & Technology Flow-chart 45 p l t p. l p l rp p m p vp p n rq p. q lp pn rqp k mp r l p r l p p tsp p. v p v p ll rp l l m p p p p p p. ll p rl p rq p p rl l m p v vp p v p m. 3.2.3. ˆp v ( ) t ˆ l mp, Fig. 3l ˆl. 1998 The Research Foundation of State University of New Yorkl p o l ˆ p lrv l rn p eqp ˆ pn q~ ol. rq~ ˆ l rv, rqq p rnk, rq rrl op t plp, p 1999 Futaba Corpp -ˆ, 2002 Sony Corpp k -ˆ ~, 2004 C.R.F Societa Consortrile per Azionip lv-ˆ ~ p ~, 2000 Midwest Research Institutep ˆ, 2001 Sony Corpp lp ˆ, 2003 Toyota Motro CorpPp l- sp rq~m p ˆ pn s~ 2001 Sony Corpp ˆl m p oq p, 2001 (t) p ˆ s Ž, 2003 Nissan Motor Co Ltdp pp s Ž ˆ q~p sl op t p p. ˆ pp Iijimal p }pp p lvp ƒv pnl ˆ v m vp. ˆ p p p v p l l rq p p p lvp l v m. l AC Dillonl p p rq lv, rp l qv e rp 4.0 wt.% pp rql kvv l. v ˆ v p lr r lp, pp p ˆl qp rpp p n l 10 wt.% rq p p. ˆ pn rqp ˆ q~ v l p rq p q p p m. 3.2.4. ˆop v ( ) t ˆo l l Fig. 4l ˆl. 1997 Matsushita Electric Ind Co Ltd Japan Science & Technology Corpl p o l l p p v p ˆo eqp, 1998 Agency of Ind Science & Technolp ˆp o l r ˆo, 1999 Toshiba Corpp l v ˆo, 2000 Toyota Motor Corpp o l l p r mlp p ˆo, 2001 Sony Corpp l rq p ˆ o, Denso Corpp nl ˆ p ˆ o, Showa Denko KKp l Žp p ˆ o, 2002 Sony Corpp ˆo-k ~, (t)lplž vp p p (Ž) ˆo, Sony Corpp ˆ, 2003 ˆp n tv ˆp ˆo p p l. r~rp ˆol ˆp r ˆ l vp p, ˆ v ˆp ˆvp ~l p t p ppp pl. ˆo ˆm l ~ s ˆ qp. ˆo m l p l l m p rnp plvv k. v ˆ o lv plr pl l d p vp, rqp deˆ p. v, p ˆo rs l rpp vp p l p p. v ˆ o v p v p, p ˆo rq p. sp ˆo 1000 ~ 2000 m 2 /g rp rp v, r ˆo pp 3000 m 2 /g d p pp, p p rqp pp p m. ˆo pn rqp ˆop rsm p pp k p m. l tn opl tn ql l k. tn op l pl Sony Corp, Toyota Motor Corp, Nissan Motor Co Ltdp n 90 t l op ˆ q rl ~ p mlp p. pt Toyota Motor Corp Nissan Motor Co Ltdp n r p q sp tep q l e q Full Electric Vehiclep r p o t l p v mpp pl.
46 Soo-Jin Park et al. / Carbon Letters Vol. 9, No. 1 (2008) 35-46, tn qp ˆ, l, ˆ ˆop r r m p ee mp, p ˆp n p rl l p pp p, lp n rl rq p, ˆ p n l p v p l p p p p, vp ˆop n p lm p pp p p r p m l k. vv ˆq ˆq~p 1.0 wt.% p p rqp ln p p plv, ˆm v v, rp p v ~ p n, l ql v, r 2.0 wt.%l 4.0 wt.% rq p p. p rp/ˆ ~ p ˆq p rqp p n p p, r } l DOE (lv)p p ml 6.5 wt.% pp rqp pp p Ž. tqp t l r tp p p n, vp q p,, k, n q, r, lv p l ~p vrp e Œq lv rql pl k p Ž. q oprqop Connect Korea lp vop k p TLOlp p p ro l p l q l pn md. p l()p p vop 21 Žlll(lvl)p p p l d. 3FGFSFODFT [1] Dillon, A. C.; Jones, K. M.; Bwkkedahl, T. A.; Kiang, C. H.; Bethune, D. S.; Heben, M. J. Nature 1997, 386, 377. [2] Bansal, R. C.; Goyal, M. Activated Carbon Adsorption, CRC Press, Boca Raton, 2005. [3] Lueking, A. D.; Pan, L.; Narayanan, D. L.; Clifford, C. E. B. J. Phys. Chem. B 2005, 109, 12710. [4] Lueking, A. D.; Yang, R. T. Appl. Catal. A 2004, 265, 259. [5] Li, Y.; Yang, R. T. J. Am. Chem. Soc. 2006, 128, 8136. [6] Yang, R. T. Carbon 2000, 38, 623. [7] Kim, B. J.; Park, S. J. Nanotechnology 2006, 17, 4395. [8] Kim, B. J.; Park, S. J. J. Colloid Interface Sci. 2007, 311, 619. [9] Kim, B. K.; Ryu, S. K.; Kim, B. J.; Park, S. J. J. Ind. Eng. Chem. 2006, 12, 121. [10] Yoo, E.; Gao, L.; Komatsu, T.; Yagai, N.; Arai, K.; Yamazaki, T.; Matsuishi, K.; Matsumoto, T.; Nakamura, J. J. Phys. Chem. B 2004, 108, 18903. [11] http://www.h2.re.kr/1herc_info/outline.htm [12] Toyota Central Res & Dev Lab Inc., Porous activated carbon for hydrogen storage and manufacturing method thereof, JP-2003-277037 [13] Yazaki Corp., Graphite Intercalating compound, JP-1989-204013. [14] Alsin Seiki Co. Ltd, Hydrogen storage materials and its manufacturing method, JP-2003-311149. [15] Enernext, LLC, Method for sorption and desorption of molecular gas contained by storage sites of nano-filament laded reticulated aerogel, US-6,906,003. [16] Futaba Corp., Method for producing hydrogen occlusion material, US-6,602,485. [17] Carnegie Mellon Univ., Process for the preparation of nanostructured materials, US-7,056,455. [18] Asahi Kasei Corp., New carbon grain of nanosized, and production method thereof, JP-2004-182509