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1 ATICLES PUBLISHED NLINE: 19 JUNE 2017 DI: /NMAT4919 Universl quinone eletrodes f long yle life queous rehrgeble btteries Ynling Ling 1, Yn Jing 1, Smn Gheytni 1, Kun-Yi Lee 1, Ping Liu 2, Antonio Fhetti 3 * nd Yn Yo 1,4 * Aqueous rehrgeble btteries provide the sfety, robustness, ffdbility, nd environmentl friendliness neessry f grid stge nd eletri vehile opertions, but their doption is plgued by po yle life due to the struturl nd hemil instbility of the node mterils. Here we rept quinones s stble node mterils by exploiting their struturlly stble ion-odintion hrge stge mehnism nd hemil inertness towrds queous eletrolytes. Upon rtionl seletion/design of quinone strutures, we demonstrte three systems tht oupled with industrilly estblished thodes nd eletrolytes exhibit long yle life (up to 3,000 yles/3,500 h), fst kinetis ( 20C), high node speifi pity (up to mah g 1 ), nd severl exmples of stte-of-the-rt speifi energy/energy density (up to Wh kg 1 / Wh l 1 ) f severl opertionl ph vlues ( 1 to 15), hrge rrier speies (H +, Li +, N +, K +, Mg 2+ ), temperture ( 35 to 25 C), nd tmosphere (with/without 2 ), mking them universl node pproh f ny queous bttery tehnology. The inresing demnd f integrtion of eletriity generted from renewble energies into the grid nd eletrifition of trnspttion vehiles ll f btteries tht re environmentlly friendly, sfe, inexpensive, nd long lsting 1,2. Aqueous rehrgeble btteries 3 6 feturing low-ost nd nonflmmble wter-bsed eletrolytes re intrinsilly sfe nd do not rely hevily on the protetion from omplex bttery mngement systems, thereby providing robustness nd ost dvntges over ompeting lithium-ion btteries tht use voltile gni eletrolytes nd re responsible f reent tstrophi explosions. However, stte-ofthe-rt queous rehrgeble btteries show sht yle life 7 nd fll sht of meeting lrge-sle pplitions where frequent replement of btteries is undesirble. The node mterils hve been the yle-life-limiting omponent f most, if not ll, queous rehrgeble btteries F exmple, led-bsed idi btteries re inexpensive nd relible but hve po yle life (200 yles f deep yling 7 ) due to the premture geing of the led (Pb) node into thik PbS 4 pssivtion lyer 8. No other frdi eletrode mteril hs been disovered to wk s node f id btteries. eent effts to substitute Pb with non-frdi tivted rbon (AC) extend yle life t the ost of 60% redution in speifi energy Another estblished fmily of queous rehrgeble btteries re nikel-bsed lkline btteries, inluding nikel iron, nikel dmium, nikel zin, nd nikel metl hydride (MmH) btteries, whih onsist of the sme nikel hydroxide (Ni(H) 2 ) thode but vrying nodes 10,14. However, iron, dmium, nd zin nodes undergo dissolution preipittion, while MmH volume expnsion ontrtion during bttery hrge dishrge yling negtively impts yle life. The omprtively most stble MmH is mde of rre erth metls nd the expensive oblt, with the ltter ounting f one-hlf of the totl mteril ost f nikel MmH bttery 15. The emerging queous lithiumion btteries (ALIBs) use less rosive, ner-neutrl eletrolytes nd ste hrge vi n ion interltion mehnism where the struture of the eletrode mteril does not lter signifintly Therefe, ALIBs ould hieve muh longer yle life thn those of their ommeril idi nd lkline siblings. However, the only two prtil nodes f ALIBs, lithium metl phosphtes 9,20 nd polyimides 21,22, re unstble to oxygen nd lklis, respetively, severely restriting pplitions. Finlly, reent developments of queous sodium-ion btteries highlight the use of low-ost nd highly stble AC nd Prussin Blue nodes; however, both pprohes exhibit very low pities ( 50 mah g 1 ) (refs 23,24). With the lk of node mterils meeting ll requirements, the pplition of queous rehrgeble btteries f lrge-sle energy stge hs been stgnnt. The mj hllenges f queous nodes lie in the serh f mterils tht re hemilly robust towrds queous eletrolytes, esily essible nd inexpensive, hve high speifi pity, ste hrge vi struturlly reversible/stble mehnism, nd fit in the eletrohemil stbility window of the eletrolyte solvent, thus wter. Quinones, of whih the most ommon motif omprises the 1,2-benzoquinone 1,4-benzoquinone units (Fig. 1), hve been onsidered f nonqueous metl-ion btteries nd queous flow btteries These ompounds ste hrge vi n ionodintion mehnism where the tions odinte to the negtively hrged oxygen toms upon eletrohemil redution of the rbonyl groups, nd unodinte reversibly during the reverse oxidtion (Fig. 1; not to be onfused with quinone derivtives where the rbonyls re onverted to redox-intive groups 31 ). Properly funtionlized quinones hve shown exellent hemil stbility 30 nd their redution potentils n be redily tuned from 1.7 to 3.2 V versus Li upon moleulr engineering 27. Despite these dvntges, there re only very few pioneering repts on their use in queous btteries. Alt et l. investigted tetrhlo-1,4- benzoquinone (TCBQ) in 2 M sulfuri id nd demonstrted 1 Deprtment of Eletril & Computer Engineering nd Mterils Siene nd Engineering Progrm, University of Houston, Houston, Texs 77204, USA. 2 Deprtment of NnoEngineering, University of Clifni, Sn Diego, Clifni 92093, USA. 3 Deprtment of Chemistry nd the Mterils eserh Center, Nthwestern University, Evnston, Illinois 60208, USA. 4 Texs Center f Superondutivity, University of Houston, Houston, Texs 77204, USA. *e-mil: -fhetti@nthwestern.edu; yyo4@uh.edu NATUE MATEIALS ADVANCE NLINE PUBLICATIN 1

2 ATICLES NATUE MATEIALS DI: /NMAT4919 Dishrge e Anode ( ) Cthode (+) 2e, 2M + + 2e, + 2M + M + M + M M Aid eletrolytes Neutrl eletrolytes Alkline eletrolytes Pb 2 2e 2, S 4 +2e 2, +S 4 + 2H 2, 4H + +4H +, H 2 PbS 4 Mn 2 4 e, Li + +e, +Li + LiMn 2 4 NiH e, H+ +e, +H + Ni(H) 2 Chrge e Figure 1 Shemtis of queous rehrgeble btteries bsed on quinone nodes operting t different ph vlues with the indited responding redox hemistries. n the node side (left pnel) is shown the redox/ion-odintion retion of 1,2-benzoquinone (left) nd 1,4-benzoquinone (right) strutures. Quinone nodes n be used in id, neutrl, nd lkline eletrolytes (middle pnel). Depending on the hoie of the eletrolyte, wide rnge of thode mterils inluding the industrilly mture Pb 2 (id), LiMn 2 4 (neutrl), nd Ni(H) 2 (lkline) n be used to omplete bttery. The responding thode retions re shown in the right pnel. stble hrge dishrge yling of 50 yles 32. The redox potentil of TCBQ is so high (0.91 V versus SHE) tht it ws used s thode mteril. Nishide s group repted 9,10-nthrquinones s node mterils f lkline polymer oxygen btteries 33 ; unftuntely, the ell lost 9% of the initil pity fter 300 yles/25 h. These wks hinted t the promise of quinone redox hemistry nd struturl stbility; however, signifint mteril innovtion is needed f optiml perfmne nd brod pplibility. Therefe, befe the seletion/syntheti efft of optiml quinones f our sope, we hve identified severl guidelines f quinone design. First, the redution potentil should pproh, but not be lower thn, the potentil f the hydrogen evolution retion [HE, ( 59 ph) V versus SHE] so s to mximize ell voltge without using wter eletrolysis. Seond, the node speifi pity should be t lest 200 mah g 1 to enhne speifi energy. Third, on top of the hemil stbility, the solubility of both oxidized /redued quinone speies should be suffiiently low in the seleted queous eletrolytes to prevent mteril loss by dissolution during yling 29. Here we rept on the use of quinones s high-perfmne node mterils f queous rehrgeble btteries feturing overll hrteristis unmet by those deriving from the ombintion of severl other lsses. To demonstrte universl generlity to the eletrolyte medium, quinone nodes were oupled with vrious industrilly mture thode mterils, suh s led oxide (Pb 2, idi onditions), spinel lithium mngnese oxide (LiMn 2 4, nerneutrl onditions), nd Ni(H) 2 (lkline onditions) (Fig. 1). ur results demonstrte tht ells bsed on rtionlly seleted/designed quinone nodes exhibit long yle life (up to 3,000 yles/3,500 h), high node speifi pity (up to mah g 1 ), fst kinetis (67 84% hrge/dishrge pity t 10C), nd stteof-the-rt speifi energy/energy densities (up to Wh kg 1 / Wh l 1 ) f severl ph onditions ( 1 to 15), hrge rrier speies (H +, Li +, N +, K +, Mg 2+ ), temperture ( 35 to 25 C), nd tmosphere (with/without 2 ). Quinone seletion f different bttery tehnologies We first rept on the seletion of suitble quinone strutures using n idi medium nd then demonstrte tht three quinones re exellent ndidtes f brod pplibility. Detils of quinone synthesis re repted in the Supplementry Infmtion (see Synthesis of quinones nd Supplementry Figs 1 13 f quinone struturl hrteriztion). Briefly, the synthesized quinones ( 5 µm in size, Supplementry Fig. 14) were mixed with ondutive rbons nd pressed into disk eletrodes with n tive mss rnging from 2.2 to 37 mg m 2. Eletrode/ell fbrition nd mesurements re desribed in the Methods setion. Coin ells re typilly used f both three-eletrode hlf-ell nd two-eletrode full-ell mesurements. Tble 1 ollets the mj perfmne prmeters f the optiml quinones fbrited here s well s those of referene mterils operting in idi (Entries 1 3), slightly idi (Entry 4), neutrl (Entries 5 8), slightly lkline (Entry 9), nd lkline (Entry 10 12) eletrolyte solutions. Quinone-bsed idi btteries In preliminry experiments the eletrohemil retion of severl simple quinones in 4.4 M sulfuri id ( lose pproximtion of the bttery id used in ommeril Pb-id btteries) ws studied. The moleulr strutures nd the potentil pity dt f the me promising quinones re shown in Fig. 2. Most quinones show redution potentil within V versus SHE, nd theetil speifi pities of mah g 1. Beuse the ell voltge is determined by the potentil differene between the node nd the thode, these quinone nodes will enble full-ell voltges of V when oupled with Pb 2 thode (1.78 V versus SHE). Suh voltges re omprble to the 1.30 V f the AC Pb 2 hybrid nd 25 45% lower thn the 2.1 V f Pb Pb 2. From the plots of Fig. 2b nd Supplementry Fig. 15 the plteu-shped voltge profiles f these quinones lerly provide stble voltge output, whih is fr me desirble thn the sloping profile f the nonfrdi AC. Among these ndidtes, pyrene-4,5,9,10-tetrone 34 (PT, red struture in Fig. 2) stnds out due to the ombintion of very high theetil speifi pity (409 mah g 1 ) nd resonbly low redution potentil (0.5 V versus SHE) (Entry 1 in Tble 1). Imptntly, the lrge plnr struture of PT will lso render the moleule less soluble thn the other quinones, whih is n essentil feture f stble opertion. The glvnostti hrge dishrge profile of our PT Pb 2 idi ell t 40 ma g 1 is shown in Fig. 2b, whih exhibits speifi pity of 395 mah g 1 (>300% nd 700% higher thn those of Pb nd AC, respetively, Fig. 2b nd Entries 2 nd 3). The very high pity of PT effetively ompenstes the 5 V higher 2 NATUE MATEIALS ADVANCE NLINE PUBLICATIN

3 NATUE MATEIALS DI: /NMAT4919 ATICLES Tble 1 Eletrohemil hrteristis, bttery onfigurtion nd perfmne prmeters of quinones versus other mterils. Entry ph Anode Chrge rrier edution potentil, (V versus SHE) Speifi pity (mah g 1 ) Cthode Speifi energy (Wh kg 1 ) Energy density (Wh l 1 ) Cyling stbility (pity%@yle number (yled time)) 1 1 PT H Pb %@1,500 (1,200 h) This wk 2 1 Pb 2 S Pb %@240 (4,500 h) AC H Pb %@3,000 (5,500 h) PPT Mg CuHCF %@1,000 (1,600 h) This wk 5 7 PPT Li LiMn %@3,000 (3,500 h) This wk 6 7 PPT N N 3 V 2 (P 4 ) %@80 (150 h) This wk 7 7 LiTi 2 (P 4 ) 3 Li LiMn %@1,200 (1,600 h) Polyimide Li LiMn %@50,000 (950 h) PPT Li LiCo %@700 (1,200 h) This wk PAQS K Ni(H) %@1,350 (2,300 h) This wk MmH H Ni(H) %@1,300 (n/) Zn H Ni(H) %@300 (800 h) 7 F the node mteril. Determined from three-eletrode glvnostti hrge dishrge mesurements. F bttery onsisting of node/thode mterils nd (if involved in the retion) eletrolyte. The unusully long time f the smll yle number is due to the slow dishrge (C/5) nd hrge (C/16) required f sustining yle life. ef. redox potentil thn tht of Pb, resulting in unompromised speifi energy. Ading to the retions f PT Pb 2 (eqution (1)) nd Pb Pb 2 (eqution (2)) btteries: Pb PT-H 4 +H 2 S 4 PbS PT+2H 2 (1) Pb 2 +Pb+2H 2 S 4 2PbS 4 +2H 2 (2) PT Pb 2 bttery requires 50% less sulfuri id nd Pb to ste the sme mount of hrge. The speifi energy/energy density of PT Pb 2 bttery is 76 Wh kg 1 /161 Wh l 1 bsed on tive eletrode mterils nd eletrolyte (inluding both solute H 2 S 4 nd solvent H 2 ). These vlues re virtully identil to the 78 Wh kg 1 /171 Wh l 1 f Pb Pb 2 nd muh higher thn the 38 Wh kg 1 /37 Wh l 1 f AC Pb 2. Note tht the signifintly lower ompted density of PT thn tht of Pb (1.65 versus 4.35 g m 3 ) does not ompromise energy density signifintly beuse PT, due to its very high speifi pity, onstitutes only onsiderbly smll weight frtion (15 wt%) in the bttery (ompre with 28 wt% f Pb in Pb Pb 2 ; the weight frtion brekdown of ll bttery onfigurtions involved in this wk is summrized in Supplementry Tble 1). The redued H 2 S 4 onsumption lso ontributes to the substntil energy density. A PT Pb 2 ell yles t % depth of dishrge t 2C hrge dishrge rte (1C = 400 ma g 1 ) f me thn 1,500 yles (>1,200 h) without obvious derese in pity nd voltge (Fig. 2 nd Supplementry Fig. 16). The verge oulombi effiieny f the 1,000th 1,500th yles is 99.8%. The ell is lso stble during longer-term yling t low urrent density of C/5, with 88% pity retention fter 200 yles (>1,700 h, Supplementry Fig. 17). The stble yling perfmne is ttributed to three properties of PT. First, the solubility of PT in the eletrolyte is low ( M; ompre with M f PbS 4 ); quinones with higher solubility in id, f exmple, 2,5-dihydroxy-1,4-benzoquinone (DHBQ), suffer from fst pity dey (Supplementry Fig. 18). Seond, PT shows n ppreibly high proton diffusivity of m 2 s 1 (Supplementry Fig. 19), nd therefe does not fm ionilly insulting lyers like PbS 4 does. Third, the eletrohemil tivity f the hrgetrnsfer retion of PT is muh higher thn tht f Pb, s hrterized by the muh higher exhnge urrent density f PT eletrode (516.6 ma g 1 ) thn tht f Pb (1.41 ma g 1 ) (ref. 35) (Supplementry Fig. 20). The PT ell retins 84% of the mximum pity t very high hrge/dishrge rte of 20C (Fig. 2d), suffiient f the demnding senrios f vehile btteries suh s engine strting (up to 18C pulse dishrge) nd regenertive breking (up to 3C pulse hrge) 8,36. Therefe, we hve demonstrted tht the PT node overomes the pssivtion nd kineti problems f Pb without srifiing speifi energy/energy density like AC does. Quinone-bsed neutrl btteries The results bove prompted us to exple quinone nodes f btteries with neutrl eletrolytes, in prtiulr ALIBs. We found tht PT is soluble in neutrl eletrolytes nd undergoes fst pity dey (Supplementry Fig. 21), therefe we hve designed polymerized version of PT, nmely PPT (Fig. 3), to hieve suffiient insolubility (Entry 5). The eletrohemil perfmne of PPT is ompred with lithium titnium phosphte (LiTi 2 (P 4 ) 3 ), whih is the stte-of-the-rt node mteril f ALIBs (Entry 7). PPT shows me thn double the speifi pity of LiTi 2 (P 4 ) 3 (229 versus 103 ma g 1 ) lbeit 0.46 V higher redution potentil (Fig. 3). A PPT LiMn 2 4 ell shows n verge voltge of 1.13 V with speifi energy/energy density of 92 Wh kg 1 /208 Wh l 1, whih re omprble to those f LiTi 2 (P 4 ) 3 -LiMn 2 4 (90 Wh kg 1 /243 Wh l 1 ). emrkbly, PPT retins 80% of the initil pity nd shows no obvious hnge in voltge profile fter 3,000 deep yles t 1C (280 ma g 1, Fig. 3 nd Supplementry Fig. 22), mking it mongst the most stble node mterils f ALIBs disovered to dte. Like PT, PPT delivers fst eletrode kinetis, with 60% of the mximum pity delivered t 20C hrge/dishrge (Supplementry Fig. 23). It is notewthy tht the differene between hrge nd dishrge potentils does not inrese with inresing urrent density, trnslting into onsistently high energy effiieny even during fst hrging (Supplementry Fig. 23b). An imptnt dvntge of PPT over LiTi 2 (P 4 ) 3 nd other node mterils repted f ALIBs is its bility to suppt the oxygen yle, ommon phenomenon f ll ommeril queous rehrgeble btteries. The oxygen yle is built-in sfety mehnism where oxygen evolves from wter oxidtion by the thode t high hrge sttes, diffuses ross the eletrolyte, nd is redued by the hrged node (Fig. 3). Note, the ph of the eletrolyte medium dereses/inreses ner the thode/node due to H + /H fmtion, respetively. This mehnism spontneously protets this type of ells from overhrge nd helps to synhronize the hrge stte of ll ells in bttery pk. Previously repted ALIBs do not hve proper node to suppt the oxygen yle. LiTi 2 (P 4 ) 3 quikly deys in the presene of oxygen in the eletrolyte 9. Although polyimides re omptible with oxygen NATUE MATEIALS ADVANCE NLINE PUBLICATIN 3

4 ATICLES NATUE MATEIALS DI: /NMAT4919 Potentil (V versus SHE) AC DMBQ AQ TMBQ H NQ H Pb 2 H DHBQ BQ b Potentil (V versus SHE) AC Pb 2 PT 0.4 Pb (prtil) Pb H DHNQ PT 0.5 Pb Theetil speifi pity (mah g 1 ) 500 d Dishrge Chrge ,200 1,500 Cyle number Coulombi effiieny (%) Voltge (V) 20, 5, 1C, C/ Chrge dishrge rte (C) Figure 2 Quinone-bsed idi btteries., Chemil struture of seleted quinones investigted in this study nd their redution potentil nd theetil pity bsed on one-rbonyl one-eletron redution. The prtil speifi pities of AC nd Pb re shown f omprison. Dshed line indites the redution potentil of Pb 2. b, Glvnostti hrge dishrge profiles f PT (40 ma g 1 ), AC (50 ma g 1 ), Pb (10 ma g 1 ), nd Pb 2 (20 ma g 1 )., Cpity retention of PT Pb 2 ell during glvnostti yling t 2C. d, Cpity of PT Pb 2 ell hrged/dishrged t C/10 20C. Inset shows the voltge profiles t seleted C rtes. All dt were olleted in 4.4 M H 2 S 4. (Entry 8) (ref. 37) they re prone to rpid hydrolysis in the lolly lkline environment resulting from oxygen redution: nphthlene diimides hve hlf-lives of seonds in modertely lkline solutions (f exmple, ph 12) (ref. 38). In ontrst, quinones hve been repted to show exellent stbility in both oxygen 32 nd lkline solutions (f exmple, 5 M KH) (ref. 30). PPT in prtiulr proves to be suffiiently stble in firly lkline eletrolyte (ph 13), where it is yled f me thn 1,200 h with 83% pity retention (vide infr). Suh yling stbility igintes from the ombintion of quinone e hemil inertness, PPT po solubility, nd mide linkge resistne towrds hydrolysis in these onditions. Amides of liphti ids, whih re nlogous to PPT, hve hlf-lives of yers t neutrl ph nd bout 2 3 yers t ph of 12 (ref. 39). Note tht these hlf-lives re f mides dissolved in solutions (homogeneous retions), whih is physil stte ompletely different thn tht of our insoluble PPT (solid stte). Heterogeneous retions (nd hydrolysis in this se) n be ders of mgnitude less effiient, if negligible t ll. Furtherme, it is resonble tht n node spends less thn 10% of its lifetime under bsi onditions, onsidering tht the oxygen yle tkes ple only during the high-voltge hrging proess, thus one n expet further lifetime extension. If desired, even higher stbility my be possible by substituting the intrinsilly bse-sensitive mide linkge with me stble bridge units/groups vi lterntive polymeriztion methods. edued (hrged) PPT is reversibly oxidized by oxygen to regenerte PPT t its dishrged stte with both the voltge profile nd pity preserved (Fig. 3d). In ft, this oxygen omptibility is generl property of ll quinones fetured in this wk regrdless of the ph of the eletrolytes ( 1 to 15; Supplementry Fig. 24). The oxygen onsumption pbility of quinones mkes it possible to use high-voltge thode mterils 40 tht pproh the potentil f the oxygen evolution retion (E), enbling high voltges nd speifi pities (Supplementry Fig. 25). An ALIB ombining the high-pity PPT node nd high-voltge thode will yield up to 65% higher speifi energy thn those of the stte-of-the-rt ALIBs. ther queous metl-ion btteries enbled by PPT In ddition to the neutrl ALIB desribed bove, we were ble to prototype severl other interesting queous metl-ion btteries bsed on PPT node nd ner-neutrl eletrolytes. This is possible due to the high tolerne of PPT f eletrolytes with different ph nd tioni speies. Thus, n lkline ALIB feturing n lkline Li 2 S 4 eletrolyte (ph = 13), PPT node, nd LiCo 2 thode (Entry 9) exhibits high node speifi pity of 200 mah g 1, n energy density of 180 Wh l 1, nd retins 83% of the initil pity f me thn 700 yles/1,200 h (Supplementry Fig. 26). Being ble to use reltively lkline eletrolytes signifintly expnds the hoie of thode mterils whih would otherwise suffer from proton-indued dysfuntion in neutrl eletrolytes 41. Furtherme, 4 NATUE MATEIALS ADVANCE NLINE PUBLICATIN

5 NATUE MATEIALS DI: /NMAT4919 ATICLES Potentil (V versus SHE) H N N H PPT LiTi 2 (P 4 ) 3 LiMn 2 4 n b Chrge Dishrge ,000 2,000 3,000 Cyle number Coulombi effiieny (%) Li 1 x Co 2 * H 2 H PPT Li + e H + 2 PPT-Li 4 d Potentil (V versus SHE) h in 2 e Time (h) Figure 3 Quinone-bsed metl-ion neutrl btteries., Chemil struture of PPT. Glvnostti hrge dishrge profiles f PPT (280 ma g 1 ), LiTi 2 (P 4 ) 3 (120 ma g 1 ), nd LiMn 2 4 (140 ma g 1 ) in 2.5 M Li 2 S 4 (ph = 7). b, Cpity retention of LiMn 2 4 PPT ell during glvnostti yling t 1C in 2.5 M Li 2 S 4 (ph 7)., Shemti explining the oxygen yle in ALIBs: H 2 is oxidized t the tlyti sites ( ) on the thode (f exmple, LiCo 2 ) to generte 2 nd H + ; the ltter is then redued by the hrged node (f exmple, PPT-Li 4 ) to ffd H. d, xygen onsumption by hrged PPT: PPT eletrode is first eletrohemilly dishrged (oxidized) nd hrged (redued) under Ar f one yle, then left to rest under 2, nd finlly put under Ar nd hrged gin. we repled lithium in ALIBs with the low-ost nd Erth-bundnt sodium to onstrut queous sodium-ion btteries (ASIBs) 23,42. This tehnology my find pplition in res where ost nd stbility, nd not energy density, my be of primry imptne. A prototype quinone-bsed ASIB with the PPT sodium vndium phosphte (N 3 V 2 (P 4 ) 3 ) onfigurtion shows high node speifi pity (201 mah g 1 ) nd 79% retention fter 80 yles in neutrl sodium nitrte eletrolyte (Entry 6, Supplementry Fig. 27), lthough the energy density (80 Wh l 1 ) is modest s limited by the low speifi pity nd potentil of N 3 V 2 (P 4 ) 3 (52 mah g 1 t 0.65 V versus SHE). Finlly, we hve expled f the first time the fesibility of n queous mgnesium-ion bttery (AMIB). The suess of n AMIB relies on the id omptibility of PPT (Entry 4 nd Supplementry Fig. 28) onsidering tht ll queous mgnesium eletrolytes re notiebly idi due to prtil Mg 2+ hydrolysis. We hve ssembled n AMIB using PPT s the node nd Prussin blue nlogue/mgnesited opper hexynoferrte (Mg x CuHCF) (ref. 43) s the thode whih shows stble yling perfmne (66% retention fter 1,000 yles) nd unommonly fst kinetis f rehrgeble mgnesium bttery (85% of mximum pity t 2C; 1C = 140 ma g 1 ; Supplementry Fig. 29). Quinone-bsed lkline btteries We further expnded quinone nodes in even me lkline eletrolytes (ph > 14) in onjuntion with the highly industrilly mture Ni(H) 2 /nikel oxyhydroxide (NiH) thode (Entry 10). Sine lkline eletrolytes hve low-lying HE potentils, our quinone of hoie f n lkline bttery is n nthrquinone-bsed polymer, poly(nthrquinonyl sulfide) 44 (PAQS), whih hs 0.54 V me negtive redution potentil thn tht of PPT. The retions f PAQS Ni(H) 2 (eqution (3)) nd MmH Ni(H) 2 (eqution (4)) re Ni(H) 2 +(0.5/n)PAQS+KH NiH+(0.5/n)PAQS-K 2 +2H 2 (3) Ni(H) 2 +Mm NiH+MmH (4) where n is the degree of polymeriztion of PAQS. At room temperture, PAQS shows speifi pity of 200 mah g 1 in 10 M potssium hydroxide (KH) (Fig. 4). Beuse of the onsumption of the KH eletrolyte, the speifi energy/energy density of PAQS Ni(H) 2 (79 Wh kg 1 /138 Wh l 1 ) re not s high s those of MmH Ni(H) 2 ( 180 Wh kg 1 /597 Wh l 1 ; Entry 11) but omprble to those of PT Pb 2. By ompring the voltge profiles of PAQS nd MmH eletrodes it is ler tht there is muh room f further lowering the redution potentil of the quinone node befe hydrogen would evolve. F exmple, quinone with the pity of PT but redution potentil 0.2 V lower thn tht of PAQS would yield muh higher speifi energy/energy density of 115 Wh kg 1 /203 Wh l 1. A PAQS Ni(H) 2 ell yled t % depth of dishrge f 1,350 yles t 1C (200 ma g 1 ) with n 88% pity retention (Fig. 4b). The bsene of notieble hnge in the hrge dishrge profile (Supplementry Fig. 30) fter prolonged yling reflets the exellent stbility of the eletrode in these extreme onditions. Suh stbility NATUE MATEIALS ADVANCE NLINE PUBLICATIN 5

6 ATICLES NATUE MATEIALS DI: /NMAT Ni(H) 2 b 250 Potentil (V versus SHE) S n PAQS MmH Chrge Dishrge , Coulombi effiieny (%) Cyle number Exhnge urrent density (ma g 1 ) Temperture ( C) PAQS MnH /Temperture (K 1 ) Chrge-trnsfer resistne (Ω g) d Voltge (V) 25 C 25 C C 25 C Chrge dishrge rte (C) Figure 4 Quinone-bsed lkline btteries., Glvnostti hrge dishrge profiles of PAQS ( ma g 1 ), MmH (150 ma g 1 ), nd Ni(H) 2 (40 ma g 1 ). b, Cpity retention of PAQS Ni(H) 2 ell during glvnostti yling t 1C., Exhnge urrent density nd hrge-trnsfer resistne of PAQS nd MmH eletrodes s funtion of temperture (dt f MmH retrieved from ref. 48). d, Cpity of PAQS Ni(H) 2 ell hrged/dishrged t C/2 20C t 25 C nd C/2 10C t 25 C. Inset shows the voltge profiles t C/2. All dt here were olleted in 10 M KH. outperfms those of the most optimized metl hydrides (80% retention fter 1,300 yles 45 ). Like PPT, PAQS lso funtions with vrious metl tions. Sodium hydroxide nd lithium hydroxide re both plusible eletrolytes f PAQS Ni(H) 2 bttery in ddition to KH (Supplementry Fig. 31). Suh tolerne llows the use of mixed hydroxide eletrolytes to ustomize bttery perfmne, ommon prtie f the nikel metl hydride bttery tehnology 46. PAQS lso ddresses one of the mj disdvntges of nikel MmH btteries tht is, drsti redution in eletrohemil perfmne t low tempertures. Most ommeril MmH Ni(H) 2 btteries deliver only 50% of the nominl energy nd n rrely dishrge beyond C/2 t 25 C (ref. 47). This perfmne redution igintes from the lrge hrge-trnsfer resistne f the redox retion of MmH, whih inreses by s temperture dereses from 25 to 40 C (ref. 48). In omprison, the hrge-trnsfer resistne f PAQS only doubles from 25 to 35 C (hrterized by eletrohemil impedne spetrosopy; Fig. 4 nd Supplementry Fig. 32). The tivtion energy f the redox retion of PAQS, lulted from the Arrhenius eqution of the hrge-trnsfer resistne versus temperture dependene, is s low s 8 kj mol 1 (ompre with 39 kj mol 1 f MmH), implying little perfmne dependene on temperture. The exhnge urrent density of the two eletrodes reitertes the different dependene of the eletrohemil tivity on temperture f the two mterils (Fig. 4 nd Supplementry Fig. 32b). Consequently, PAQS experienes mere 7% redution in pity s the temperture dereses from 25 to 25 C, nd the voltge gp between hrge nd dishrge t C/2 (1C = 225 ma g 1 ) inreses only slightly from 101 to 127 mv (Fig. 4d). Imptntly, the rte pbility of PAQS is onsistently high regrdless of temperture, with 93 nd 86% pity remining t 10C hrge/dishrge t 25 nd 25 C, respetively (Fig. 4d nd Supplementry Fig. 33). Chllenges nd opptunities of quinone nodes Figure 5 summrizes the redution potentil versus ph of PT, PPT, nd PAQS eletrodes in Pourbix digrm. The medi t whih our quinones operte spn very wide ph rnge, from strongly idi through neutrl to strongly lkline. From the plot it is ler tht t every ph vlue these quinones pproh the HE potentil nd still hve room f further improvement. F 1 < ph < 1, the redution potentils of ll three quinones re ph-dependent nd derese by 59 mv per ph inrement, inditing proton stge mehnism where one proton is sted f every injeted eletron nd vie vers. As the ph inreses bove 3, the onentrtion of proton dereses to suh n extent tht metl-ion stge beomes dominnt nd the redution potentil beomes ph-independent. Indeed, ompositionl nlysis vi indutively oupled plsm method f PPT eletrode hrged (eletrohemilly redued) in Li 2 S 4 (ph 7) eletrolyte solution ws perfmed nd onfirmed tht virtully ll ( 97%) of the injeted hrge ws blned by lithium ions insted of protons (see detils in Methods). 6 NATUE MATEIALS ADVANCE NLINE PUBLICATIN

7 NATUE MATEIALS DI: /NMAT4919 ATICLES Quinone Pb btteries Quinone-bsed metl-ion btteries Quinone nikel btteries (Pb 2 ) Potentil (V versus SHE) PT (CuHCF) PPT (LiMn 2 4 ) PPT (LiCo 2 ) PPT (NiH) PAQS E HE ph b Fst hrgebility Energy density Cyle life pertion ph rnge Energy density Cyle life Low-temperture perfmne Energy density Cyle life Environmentl friendliness Avilbility xygen omptibility Avilbility Fst hrgebility Avilbility Affdbility Affdbility Affdbility PT Pb AC PPT LiTi 2 (P 4 ) 3 Polyimide PAQS MmH Zn Figure 5 Comprison of node mterils f queous rehrgeble btteries., Creltion between the redution potentils of quinone eletrodes mesured with yli voltmmetry nd the ph vlue of queous eletrolytes. The bttery drwings depit plusible bttery onfigurtions bsed on quinone nodes nd suitble thodes. They re positioned t the ph rnge where the desribed btteries operte. The top nd bottom of the bttery drwings denote the end-of-hrge potentil f the thode nd node, respetively. Lrger symbols highlight the dt points diretly relted to the quinone ph ombintions studied in the btteries. Grey dshed lines show the thermodynmi potentil f 2 (E) nd H 2 (HE) evolution with ph. b, Itemized omprison of quinones with existing node mterils f idi btteries (AC nd Pb), ALIBs (LiTi 2 (P 4 ) 3 nd imide), nd lkline btteries (MmH nd Zn). Finlly, Fig. 5b nd Supplementry Tble 2 ompre some of the most imptnt eletrode prmeters f quinones nd ompeting ommeril nd emerging node mterils, inluding Pb, AC (both f idi btteries), LiTi 2 (P 4 ) 3, polyimide (both f ALIBs), MmH, nd Zn (Entry 12) (both f lkline btteries). Quinone nodes deliver speifi pity nd energy density vlues tht n mth exeed those of severl existing node mterils (Supplementry Fig. 34). However, struturl modifition of these quinoid es/strutures with, f instne, simple eletron-donting gni funtionlities n overome one of the mj limittions of the three exmples repted here, whih is the reltively high redution potentil. Thus, optimized quinones retining PT speifi pity but with lower redution potentils ombined with resonbly improved thodes my further inrese the speifi energy/energy density of quinone-bsed btteries to Wh kg 1 / Wh l 1, most of whih vlues re unhievble with other existing nodes (Supplementry Fig. 34b). Furtherme, polymeriztion protools ffding mromoleules with even higher moleulr weights, thus lower solubility, s well s different quinone unit onnetivities ould further enhne ell stbility. However, our quinones lredy lerly demonstrte exellent yle life nd without vilbility/ost/environmentl issues tht some hevy metls nd phosphtes experiene 49,50. Their fst eletrode kinetis nd effiient hrge trnspt ensure high power nd fst hrgebility even t low tempertures; hene, overoming some of the mj obstles f existing id nd lkline btteries. Their suppt f the oxygen yle further dds the ritilly imptnt relibility to neutrl queous rehrgeble btteries, pving the wy towrds their prtil pplition. In onlusion, this wk demonstrtes tht regrdless of the ph of the medium, hrge rrier speies, temperture, nd tmosphere, quinones n be designed to operte s stble node mterils. Quinone nodes n be oupled with ny thode/eletrolyte ombintions f queous rehrgeble btteries. They enble btteries with long yle life, high pity, fst kinetis, s well s severl exmples of exellent energy density vlues, rendering them vible ontenders f lrge-sle energy stge. Furtherme, the possibility of struturl modifitions of quinone es with eletron-withdrwing nd/ eletron-donting substituents nd vrition of the polymeriztion protools provides n opptunity to improve ell perfmne nd stbility further. Methods Methods, inluding sttements of dt vilbility nd ny ssoited ession odes nd referenes, re vilble in the online version of this pper. eeived 11 November 2016; epted 18 April 2017; published online 19 June 2017 NATUE MATEIALS ADVANCE NLINE PUBLICATIN 7

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Pierozynski, B. n the low temperture perfmne of nikel-metl hydride (NiMH) btteries. Int. J. Eletrohem. Si. 6, (2011). 48. Senoh, H., Hr, Y., Inoue, H. & Iwkur, C. Chrge effiieny of mish metl-bsed hydrogen stge lloy eletrodes t reltively low tempertures. Eletrohim. At 46, (2001). 49. Vesbg, P. C. K. & Jrmillo, T. F. Addressing the terwtt hllenge: slbility in the supply of hemil elements f renewble energy. SC Adv. 2, (2012). 50. Cdell, D. & White, S. Pek phosphus: lrifying the key issues of vigous debte bout long-term phosphus seurity. Sustinbility 3, (2011). Aknowledgements The infmtion, dt, wk presented herein ws funded in prt by the Advned eserh Projets Ageny-Energy (APA-E), US Deprtment of Energy, under Awrd Number DE-A The queous Mg-ion bttery study ws suppted by the ffie of Nvl eserh Young Investigt Awrd (N ). The queous N-ion bttery study ws suppted by the Ntionl Siene Foundtion (NSF CMMI ). This reserh used resoures of the Advned Photon Soure, US Deprtment of Energy (DE) ffie of Siene User Fility operted f the DE ffie of Siene by Argonne Ntionl Lbty under Contrt No. DE-AC02-06CH A.F. thnks the Shenzhen Peok Pln projet (KQTD ) f suppt. We thnk J. Xu nd E.. Buiel f helpful disussions nd Z. Meng f the help on fbriting lkline btteries. Auth ontributions Y.Y. nd Y.L. oneived this wk; Y.L., P.L. nd Y.Y. designed the experiments; Y.L., Y.J. nd S.G. synthesized the mterils; Y.L., Y.J., S.G. nd K.-Y.L. rried out the eletrohemil mesurements; A.F. nd Y.L. perfmed the bttery mteril ost nlysis; Y.Y. nd A.F. direted the projet; Y.L., A.F. nd Y.Y. o-wrote the pper; ll uths nlysed the results nd ommented on the mnusript. Additionl infmtion Supplementry infmtion is vilble in the online version of the pper. eprints nd permissions infmtion is vilble online t Publisher s note: Springer Nture remins neutrl with regrd to jurisditionl lims in published mps nd institutionl ffilitions. Crespondene nd requests f mterils should be ddressed to A.F. Y.Y. Competing finnil interests Y.Y. nd Y.L. re invents of ptent pplitions (US/2014/ , US/2016/ ) on the neutrl nd lkline btteries desribed herein. Y.Y., Y.L., S.G. nd Y.J. re invents of ptent pplition (US/62/165,377) on the id btteries. A.F. hs no ompeting interests. 8 NATUE MATEIALS ADVANCE NLINE PUBLICATIN

9 NATUE MATEIALS DI: /NMAT4919 Methods Fbrition of quinone eletrodes. Quinones shown in Fig. 2 were mixed with hydrophili multi-wlled rbon nnotubes (CH-funtionlized, µm in length, nm in dimeter; US eserh Nnomterils) in 1:1 rtio (ll rtios re repted by weight unless speified otherwise) 14 with the id of H 2, dried under vuum, nd pressed to fm disk eletrodes with the rel mss loding being 16 mg m 2. PPT, Super P rbon (TIMCAL), nd polytetrfluoethylene (MTI) were mixed in 6:3:1 rtio with the id of ethnol, pressed into stinless steel mesh disk (type 316), nd dried in vuum. The rel mss loding of PPT in the eletrode is 2.2 mg m 2. PAQS, Super P rbon, nd polytetrfluoethylene were mixed in 7:2:1 rtio with the id of H 2, nd the resulting mixture ws pressed nd dried under vuum to fm eletrodes. The rel mss loding of PAQS in the eletrode is 37 mg m 2. The Pb eletrode ws ut from ommeril Pb-id bttery. Ativted rbon (AC) loth (KYNL) ws used s the eletrode s reeived. Crbon-oted LiTi 2 (P 4 ) 3 ws synthesized s previously repted 51. The LiTi 2 (P 4 ) 3 eletrode ws fbrited vi proedure similr to tht f PPT but with 7:2:1 rtio. The Mishmetl eletrode ws fbrited by spreding slurry of MmNi 3.69 Co 0.72 Mn 0.40 Al 0.21 X (CXTC), Ni (T255), rboxymethyl ellulose, polyrylte sodium, nd styrene-butdiene rubber (10:0.1:09:12:0.525) in H 2 onto nikel fom followed by drying nd pressing. The eletrode ws tivted by glvnosttilly hrging dishrging t 75 ma g 1 f 10 yles nd then 150 ma g 1 f 5 yles in 8 M KH. Hlf-ell mesurements. Three-eletrode hlf-ell mesurements were perfmed to determine the dependene of redution potentils of quinones on ph nd the voltge profiles of individul eletrode mterils. In prtiulr, the fmer ws mesured by yli voltmmogrm nd the ltter by glvnostti hrge dishrge. Coin ells (C2032) were used to perfm the three-eletrode mesurements. The eletrodes of interest were pled t the positive side s the wking eletrode. Ativted rbon loth served s the ounter eletrode t the negtive side. F ph 1 to 13, Ag/AgCl (0.197 V versus SHE) served s the referene eletrode. F me lkline eletrolytes, Hg/Hg (98 V versus SHE) ws used insted. The referene eletrodes onneted to the eletrolyte vi hole t the negtive se. F ph < 1, H 2 S 4 with the desired onentrtion in H 2 ws used s the eletrolyte. F ph from 1 to 13, 1 M KCl with lulted mount of H 2 S 4 nd LiH were the eletrolytes f PT nd PAQS. F PPT studies, the suppting eletrolyte KCl ws repled by 2.5 M Li 2 S 4. F ph > 13, KH with the desired onentrtion in H 2 ws used s the eletrolyte. Glvnostti intermittent titrtion tehnique (GITT) ws used to determine the proton diffusivity in PT/PT-H x. A yled PT eletrode ws first fully dishrged (oxidized). The eletrode ws then hrged t 600 ma g 1 f 108 s nd then left f rest f 30 min. The hrging resting ws repeted until the hrge potentil rehed 0.3 V versus SHE. The ion diffusivity ws lulted s repted 28. Full-ell mesurements. The yling perfmne, rte pbility, nd temperture-dependent properties were mesured with two-eletrode full-ell set-ups. The quinone node is the pity-limiting omponent in eh of the full ells. The thodes were brought to 50% stte of hrge befe oupling with quinone eletrode. Pb 2 /PbS 4 nd NiH/Ni(H) 2 eletrodes were tken from ommeril btteries. LiMn 2 4 eletrodes were fbrited s previously repted 52. The LiCo 2 /Li x Co 2 eletrode ws fbrited from LiCo 2 powder (MTI) vi proedure similr to tht f PAQS but with n 8:1:1 rtio. N 3 V 2 (P 4 ) 3 (ref. 53) nd CuHCF (ref. 54) were synthesized nd the responding eletrodes fbrited ding to repted methods. Glss fibre pper ws used s the seprt f id nd ner-neutrl btteries, while polymide seprt ws used f lkline btteries. The seprts were wetted with the following eletrolytes: 4.4 M H 2 S 4 f id btteries; 2.5 M Li 2 S 4 (ph 7 nd 13), 5 M NN 3, 4.5 M Mg(N 3 ) 2 f queous lithium-ion, sodium-ion, nd mgnesium-ion btteries, respetively; 10 M KH f lkline btteries. Swgelok-type ells were used f id btteries, where Pb nd titnium were the urrent ollets f the thode nd node, respetively. Coin ells were used f ll other bttery onfigurtions. Exhnge urrent density of PT eletrodes. The exhnge urrent density of PT eletrodes ws mesured with miro-polriztion. A yled PT Pb 2 ell ws brought to 38% stte of hrge, left f rest f 30 min, nd then snned t 1 mv s 1 in the rnge of ±3 mv versus the equilibrium voltge. The exhnge urrent density (J 0 ) is derived from the slope ding to J 0 =J T/(F V ), where J is the mesured urrent, is the gs onstnt, T is the temperture, F is the frdi onstnt, nd V is the voltge perturbtion. Temperture-dependent properties of PAQS eletrodes. The temperture-dependent properties of PAQS eletrodes were hrterized by exhnge urrent density nd hrge-trnsfer resistne mesured with miro-polriztion nd eletrohemil impedne spetrosopy, respetively. A yled PAQS AC ell ws brought to 50% stte of hrge t room temperture. The ell ws then brought to the desired temperture nd left to rest f 30 min pri to mesurements. Eletrohemil impedne mesurements were perfmed from ATICLES khz to 5 mhz with perturbtion voltge of 3 mv. The hrge-trnsfer resistne ws fitted from the semiirle t mid frequeny. The tivtion energy ws lulted from either exhnge urrent density hrge-trnsfer resistne using the Arrhenius eqution. Eletrode omposition nlysis. The interlting ion speies in PPT hrged in 2.5 M Li 2 S 4 ws nlysed with the indutively oupled plsm (ICP) tehnique. The fbrition of eletrode nd ell followed the typil proedure desribed bove, exept tht 5 wt% of lium rbonte ws dded to the eletrode mixture s n inert internl referene. The ell ws disssembled t the fully hrged (lithited) stte. The eletrolyte on the surfe of the PPT eletrode ws briefly bsbed with weighing pper. The mixture ws srped from the stinless steel mesh urrent ollet, dried, nd digested f nlysis. There re two types of lithium ions in the eletrode: the lithium ions odinted to PPT nd those from residul Li 2 S 4. The ltter is subtrted by mesuring the onentrtion of sulfur: Li 2 S 4 is the only speies in the ell tht ontins sulfur, nd the tomi rtio of Li:S is 2:1. The rtio of odinted lithium to the host PPT nnot be diretly determined beuse none of the elements in PPT (rbon, hydrogen, oxygen, nd nitrogen) is mesurble with ICP. The internl referene lium rbonte is therefe used to indite the PPT onentrtion in the smple solution. The use of n internl referene ensures urte mesurement of lithium ontent despite inomplete trnsfer of the eletrode mteril from the urrent ollet. Energy nd power lultions. The speifi energy of ell onfigurtion (E s ) is lulted s the produt of the ell voltge (V ell ) nd ell speifi pity (C ell ) following the reent review pper Polymer-bsed gni btteries from U. S. Shubert s group 29 E s =C ell V ell (5) C ell is typilly lulted from the speifi pities of thode (C ) nd node (C ) C ell =(C 1 +C 1 ) 1 (6) Note tht C ell is lulted bsed on the weight of tive mterils tht is, the weight of inert omponents suh s pkging mterils, seprt, ondutive gent, urrent ollets, nd so on is not inluded. Therefe E s is the mximum speifi energy tht n be delivered by ell onfigurtion. A rough estimtion of tul speifi energy is to onsider tht the inert omponents dd % weight to tive mterils, thus hlving the speifi energy from the mximum 7. The weight of eletrolytes needs to be inluded f lultion when the eletrolyte is onsumed in the bttery retion (tht is, id btteries of ll fms nd quinone nikel btteries), thus C ell =(C 1 +C 1 +C 1 e ) 1 (7) where C e is the pprent speifi pity of the eletrolyte, whih is defined s C e =z F/(M w 1 ) (8) where M w is the moleulr weight of the solute tht prtiiptes in the retion (f exmple, H 2 S 4 nd KH), z is the mole number of eletrons trnsferred with the onsumption of one mole of eletrolyte solute moleule (f exmple, z =1 f Pb Pb 2 nd z =2 f PT Pb 2 ), F is the Frdy onstnt, nd is the mss onentrtion of the eletrolyte. V ell is theetilly the differene between the potentil of thode (E ) nd node (E ) V ell =E E (9) Experimentlly, V ell is usully obtined s the verge voltge between hrge nd dishrge. Speifilly f plotting the gone plot (Supplementry Fig. 14), the ell voltge is defined s the dishrge voltge so s to reflet the hnge of output voltge s the urrent density hnges. Beuse of the lk of urrent density-dependent voltge dt f some ell onfigurtions repted in literture, up to 10% overestimtion of speifi energy should be expeted in the gone plot f non-quinone-bsed btteries. In the end, the universl eqution f E s is expressed s E s =(C 1 +C 1 +C 1 e ) 1 V ell (10) Energy density (E d ) is defined s energy per totl volume of thode/node mterils nd, if involved in the retion, eletrolytes: E d =Energy/Volume (11) =(Cpity V ell )/(V +V +V e ) (12) =[C ell (W +W +W e ) V ell ]/(W /ρ +W /ρ +W e /ρ e ) (13) NATUE MATEIALS