USOO946,6839B2 (12) United States Patent (10) Patent No.: US 9,466,839 B2 Otsuka et al. (45) Date of Patent: *Oct. 11, 2016 (54) ELECTRODE ACTIVE MATERIAL FOR (52) U.S. Cl. ELECTRICITY STORAGE DEVICE, AND CPC ............... H01 M 4/60 (2013.01): HOIG II/30 ELECTRICITY STORAGE DEVICE USING (2013.01); HOIG II/48 (2013.01); H0IG SAME II/50 (2013.01); (Continued) (75) Inventors: Yu Otsuka, Osaka (JP); Nobuhiko (58) Field of Classification Search Hojo, Osaka (JP): Takafumi CPC ................................................. HO1M 1070525 Tsukagoshi, Osaka (JP); Toshiki See application file for complete search history. Nokami, Kyoto (JP); Jun-ichi Yoshida, Kyoto (JP) (56) References Cited (73) Assignee: Panasonic Corporation, Osaka (JP) U.S. PATENT DOCUMENTS 4,343,871 A 8, 1982 Tobishima et al. (*) Notice: Subject to any disclaimer, the term of this 5,143,805 A * 9/1992 Anderman .............. HO1M 2/14 patent is extended or adjusted under 35 429,217 U.S.C. 154(b) by 964 days. (Continued) This patent is Subject to a terminal dis claimer. FOREIGN PATENT DOCUMENTS EP O 911 893 A1 4f1999 (21) Appl. No.: 13/583,880 EP 1406339 A1 4/2004 (22) PCT Filed: Mar. 11, 2011 (Continued) (86). PCT No.: OTHER PUBLICATIONS S 371 (c)(1), JP 2008222559 A Translation from Espacenet.* (2), (4) Date: Sep. 10, 2012 (Continued) (87) PCT Pub. No.: WO2011/111401 Primary Examiner — Barbara Gilliam PCT Pub. Date: Sep. 15, 2011 Assistant Examiner —Nathanael Zemui (74) Attorney, Agent, or Firm — McDermott Will & (65) Prior Publication Data Emery LLP US 2013 FOOO483.6 A1 Jan. 3, 2013 (57) ABSTRACT The present invention provides an electrode active material (30) Foreign Application Priority Data for an electricity storage device, having a structure repre sented by following formula (1). In the formula (1), R to R. Mar. 12, 2010 (JP) ................................. 2010-056722 each denote independently a hydrogen atom (except for a case where all of R to Re denote hydrogen atoms), a (51) Int. Cl. halogen atom, an optionally Substituted phenyl group, an HOLM 4/60 (2006.01) optionally Substituted heterocyclic group, or an optionally HOLM 4/37 (2010.01) Substituted hydrocarbon group having 1 to 4 carbon atoms. (Continued) 21 Claims, 1 Drawing Sheet 22 15 16 7 sessessessees & F.2 122 xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxN2 SN N S St. 11 US 9,466,839 B2 Page 2 (51) Int. Cl. FOREIGN PATENT DOCUMENTS HIM IO/052 (2010.01) EP 2 234 191 A1 9, 2010 HOIG II/30 (2013.01) JP 55-161376 A 12, 1980 HOIG II/48 (2013.01) JP 56-086466 A 7, 1981 JP 4 O87258 A 3, 1992 HOIG II/52 (2013.01) JP 11-126.610 A 5, 1999 HIM IO/0566 (2010.01) JP 3O39484 B2 5, 2000 JP 3045750-82 5, 2000 HOIG II/50 (2013.01) JP 3257516 B2 2/2002 JP 2007-305430 A 11, 2007 (52) U.S. Cl. JP 2007 305430 A * 11, 2007 CPC ............. H0IM 4/137 (2013.01); H0IM 4/606 JP 2008-112630 A 5, 2008 (2013.01); H0IM 10/052 (2013.01); HOLM JP 2008-222559 A 9, 2008 10/0566 (2013.01); Y02E 60/122 (2013.01); E. E. A ck 23. Y02E 60/13 (2013.01) : 2009/118989 A1 10, 2009 WO 2010.006852 A1 1/2010 (56) References Cited U.S. PATENT DOCUMENTS OTHER PUBLICATIONS 6,413,675 T/2002 Harada et al. International Search Report issued in International Application No. 9,099,746 8, 2015 Otsuka ................ HO1M 10,052 PCT/JP2011/001448 issued on Jun. 14, 2011. 2003/O118877 6, 2003 Armand et al. Chinese Search Report issued in Application No. 2011800131500 2009,0246631 10, 2009 Hojo ................... HO1 M 4/1395 dated Apr. 23, 2014. 429,213 Extended European Search Report issued in corresponding Euro 2010.0047688 2, 2010 Ohtsuka et al. pean Patent Application No. 11753064.2, mailed on Jul. 14, 2015; 2011 O152491 6, 2011 Kawano et al. .................. 528.8 4 pages. 2013/O122367 5, 2013 Otsuka ................ HO1 M 4/5.835 429,213 * cited by examiner U.S. Patent Oct. 11, 2016 US 9,466,839 B2 FIG. 10 15 16 17 14 N226 & N \ N SS SSN As a % (2x2SX2 N3&%:33N2 NYYYYYYYYYYYYYYYYYNYYYYYYYYYYYYY. 11 12 13 18 21 Reference Example 1 omparative Example 1N O 0.2 0.4 0.6 0.8 Capacity (mAh US 9,466,839 B2 1. 2 ELECTRODE ACTIVE MATERAL FOR In this description, a compound having four ketone ELECTRICITY STORAGE DEVICE, AND groups in one molecule is referred to as a “tetraketone ELECTRICITY STORAGE DEVICE USING compound. Particularly, a compound having a pyrene ring SAME and four ketone groups introduced in the pyrene ring is referred to as an 'aromatic tetraketone compound'. RELATED APPLICATIONS CITATION LIST This application is the U.S. National Phase under 35 U.S.C. S371 of International Application No. PCT/JP/2011/ Patent Literature 001448, filed on Mar. 11, 2011, which in turn claims the 10 benefit of Japanese Application No. 2010-056722, filed on PTL 1: JP 3045750 B Mar. 12, 2010, the disclosures of which Applications are PTL 2: JP 3O39484 B incorporated by reference herein. PTL 3: JP 3257516 B PTL 4: JP 56 (1981)-86466 A TECHNICAL FIELD 15 PTL 5: JP 2007-305430 A The present invention relates to an electrode active mate SUMMARY OF INVENTION rial for an electricity storage device, and an electricity storage device in which the electrode active material is used. Technical Problem BACKGROUND ART Generally, an electricity storage device in which a known quinone organic compound is used has a much lower dis With advancement of electronic techniques, portable elec charge Voltage than the discharge Voltage (3 to 4 V) of a tronic apparatuses, such as cellular phones, portable per conventional electricity storage device in which an inorganic Sonal computers, personal data assistances (PDAS) and 25 oxide. Such as lithium cobalt oxide, is used. Thus, it is portable game machines, have been spread rapidly. Accord difficult to increase the substantial energy density of the ingly, electricity storage devices, such as secondary batter electricity storage device while using the quinone organic ies, are in an increasing demand as power Supplies for the compounds described in Patent Literatures 1 to 3 as elec portable electronic apparatuses. In order to increase the trode active materials. energy densities of the electricity storage devices, research 30 On the other hand, as a result of intensive studies, the and development for a new electrode active material is being present inventors have found that the quinone organic com carried out actively. pound described in Patent Literature 5 exhibits a high energy For example, as a candidate for the new electrode active density and high discharge potential and is promising for material, an organic compound capable of causing revers increasing the discharge Voltage of an electricity storage ibly an oxidation-reduction reaction is proposed. The 35 device. However, the compound described in Patent Litera organic compound has a specific gravity of about, for ture 5 is easily dissolved in an electrolyte of the electricity example, 1 g/cm, which is smaller than that of an inorganic storage device in some cases, and does not always have oxide. Such as lithium cobalt oxide, that has been conven sufficient properties in the viewpoint of achieving desired tionally used as an electrode active material. Thus, use of the charging and discharging cycle characteristics. organic compound as an electrode active material may make 40 The present invention is intended to provide a new it possible to develop an electricity storage device having a electrode active material that can, while having a high high energy density. Moreover, it can mitigate risks, such as energy density and high discharge potential, contribute also exhaustion of rare metal resources, resultant Soaring prices to the improvement of the charging and discharging cycle of the resources, and environmental pollution due to leakage characteristics of an electricity storage device. The present of heavy metal, because the organic compound contains no 45 invention is also intended to provide an electricity storage heavy metal. device in which the electrode active material is used. As an example of the organic compound that can be used as an electrode active material, a quinone organic compound Solution to Problem is known (Patent Literatures 1 to 3, for example). Generally, the quinone organic compound refers to an aromatic com 50 That is, the present invention provides an electrode active pound in which two ketone groups (C=O) are introduced in material for an electricity storage device, having a structure one aromatic ring. represented by the following formula (1), Patent Literature 1 describes an aqueous secondary bat tery in which a paraquinone compound and an orthoquinone compound are used as electrode active materials. The para 55 Chemical Formula 1 quinone compound is an organic compound in which two (1) ketone groups are introduced in the para position on an aromatic ring. The orthoquinone compound is an organic compound in which two ketone groups are introduced in the ortho position on an aromatic ring. Patent Literature 1 also 60 describes polymers of quinone organic compounds. On the other hand, Patent Literatures 4 and 5 each describe a non-aqueous lithium secondary battery in which a quinone organic compound is used as an electrode active material. Patent Literature 5 describes a quinone organic 65 compound (pyrene-4,5,9,10-tetraone) in which four ketone groups are introduced in a pyrene ring. US 9,466,839 B2 3 In the formula (1), R to R each denote independently a hydrogen atom (except for a case where all of R to R. Chemical Formula 4 denote hydrogen atoms), a halogen atom, an optionally (19) Rs Substituted phenyl group, an optionally Substituted hetero :: :: R10 cyclic group, or an optionally Substituted hydrocarbon group having 1 to 4 carbon atoms.