US 2017034610481 us) United States 2) Patent Application Publication co) Pub. No.: US 2017/0346104 Al Helms et al. (43) Pub. Date: Novy. 30, 2017 (64) REDOX-FLOW BATTERIES EMPLOYING (62) US.CL OLIGOMERIC ORGANIC ACTIVE CPC HOLM 8/0239 (2013.01); HOIM 8/188 MATERIALS AND SIZ CTV (201301), MICROPOROUS POLYMER MEMBRANES on ABSTRACT (71) Applicant: The Regents of the University of ee) Intermittent energy sources, including solar and wind, Berkley, CA (US); Etfeune Chenard, we show that active-species crossover can be arrested by ‘Urbana, IE (US): Nagarjuna Gavvalupali, Urbanna, TL (US Jeffrey S. Moore, Savoy, IL (US) 21) Appl. No. 15/606,961 ‘oligomeric redox active organie molecules were paired with ‘icroporous polymer membranes, the rate of active-material (22) Filed: May 26, 2017 crosscver was cither completely blocked or slowed more than 9,000-fold compared to traditional separators at mini- Application Data ‘al eost to ionie conductivity, Inthe ease ofthe later, this (G0) Provisional application No. 621342,764, filed on May corresponds to an absolute rate of ROM crossover of less 27, 2016, than 3umol em” day” (fora 1.0 M concentration gradient), \whiei exceeds performance targets recently set forth by the battery incastry This strategy was generalizable to both high GI) Ime And lows-potental ROMS in a variety of electrolytes, high: HOLM 80239 (2006.01) lighting the importance of macromolecular design in imple- HOIM 8718 (2006.01), senting next-generation redox-low batteries. Related U, ication Classification © PFs © PF = © \< an/ Rae gON® ASN tBu o / ae, Rez p-< )-o O PFs tBuPatent Application Publication Nov. 30,2017 Sheet 1 of 16 US 2017/0346104 Al a) Fig. 1Patent Application Publication Nov. 30,2017 Sheet 2 of 16 US 2017/0346104 ALPatent Application Publication Nov. 30,2017 Sheet 3 of 16 US 2017/0346104 AL a) ae de 124 © Celgard 4 Native PIM-1 104 Cross-linked PIM-1 t 384 C1 MM gj 4 24 pads an aaee 0 0 5 10 15 20 25 Fig. 3A th b) 10° [J Monomer (1a) to>] [1 Dimer (2a) Te [3 Trimer (3a) 10 7 ae te c 10°4 D!Dag a 104 104 fl cS Celgard Native PIM-1 Cross-linked . PIM-1 Fig. 3BPatent Application Publication Nov. 30,2017 Sheet 4 of 16 US 2017/0346104 Al cm, } ea ; b) 30 25 t 20 Cia! mM Celgard Cross-linked PIM-1 (Limit of quantification) ° “Oy OPF. 9 +o} Z 2 A q J UN Ny ® @ opr, © OPr. | ® Daramic = | & Crosslinked PIM-1 Oo | {Bu Bu °. Fig. 4Patent Application Publication Nov. 30,2017 Sheet 5 of 16 US 2017/0346104 Al o=112.04 | Fig. 5Patent Application Publication Nov. 30,2017 Sheet 6 of 16 US 2017/0346104 Al HOMO LUMO Fig. 6Patent Application Publication Nov. 30,2017 Sheet 7 of 16 US 2017/0346104 Al Fig. 7Patent Application Publication Nov. 30,2017 Sheet 8 of 16 US 2017/0346104 Al AG, kcal/mol 35 30 25 20 ROM" monomer 9 —— PMF for the PF, molecule 10 o 2 4 6 8&8 0 2 4 16 18 Rom - PF, distance, A Fig. 8Patent Application Publication Nov. 30,2017 Sheet 9 of 16 US 2017/0346104 Al 10 8 3S = BY —— Rom1 2+, PMF for the AN molecule oC ———— Rom1 1+, PMF for the AN molecule a 4 2 oO 2 4 6 8 10 12 14 #16 18 20 Rom - AN distance, A Fig. 9Patent Application Publication Nov. 30,2017 Sheet 10 of 16 US 2017/0346104 Al a) b) c) 24 ij ta *13a 2 Pe t ts ipa ipa iA ad 2 2 24 “ a] 5 2 mr T 6 T a “10 08 08 0A oe 06 08 ae 46 -b4 EIN EN EIN qd) e) 21 3b °13c 1 44 1) t 24 ipa] ip A ° 24 a] a4 3a T T T T T ae 45 42 98 02 04 08 08 EN EIV—> Fig. 10Patent Application Publication Nov. 30, 2017 Sheet 11 of 16 US 2017/0346104 A1 a) ipa Tess ee eran TTEers CimM — CimM — cimM — 4) e) ° 2. t 1 <° dw ~ 7 5. ‘0 0 eres es Presa s cin Crm Fig. 11Patent Application Publication Nov. 30,2017 Sheet 12 of 16 US 2017/0346104 AL , eee 4 atPatent Application Publication Nov. 30, 2017 Sheet 13 of 16 US 2017/0346104 Al Before heating 100 80 60 40 20 Transmittance (%) 3000 2500 2000 1500 1000 Wavenumber (cm) Fig. 13Patent Application Publication Nov. 30, 2017 Sheet 14 of 16 US 2017/0346104 Al Fig. 14Patent Application Publication Nov. 30, 2017 Sheet 15 of 16 US 2017/0346104 Al 25 20 7 = Celgard (75 um) _ © Cross-linked PIM (29 im) Z19 Zul Fig. 15Patent Application Publication Nov. 30,2017 Sheet 16 of 16 US 2017/0346104 AL a Oj eR RMR, ec ‘Microporous polymer membrane : feesePiorcontinca PN ROM Redox tive Ogomers RAC) ton span) cf co 0 . % : x (0) . R, 2 motes i nA . rot rd “ ay uz 5 S {E) Sorvent: Acetonitrile, DMF, OMSO, propylene carbonate, 1,2-dimethonyethane, etc Supporting Bectrotye Salt: retrasxvammonium hexafiuarophesphate salts, etreaitylammanium tetravoroborate sts, siali metal Neatuorophosphate sats, sia metal tetrafuocaborate sats, et Fig. 16US 2017/0346104 Al REDOX-FLOW BATTERIES EMPLOYING OLIGOMERIC ORGANIC ACTIVE, MATERIALS AND SIZE-SELECTIVE ‘MICROPOROUS POLYMER MEMBRANES. CROSS REFERENCE TO RELATED APPLICATIONS. [0001] This application claims priority to U.S. Provisional Application Ser. No. 62/342.764 fled May 27, 2016, which ‘application is incorporated herein by reference as if fully st Torth in their entirety ‘STATEMENT OF GOVERNMENTAL SUPPORT [0002] The invention described and claimed herein was ‘made in part utilizing funds supplied by the U.S. Department ‘of Enemy under “Contract No. DE-ACO2-05CHII231 between the U.S. Department of Energy and the Regeats of the University of California forthe management and oper tion of the Lawrence Berkeley National Laboratory. The povernment bas certain rights in this invention, BACKGROUND OF THE INVENTION Field of the Invention [0003] The present invention relates to the field of redox- flow batteries Related Art 10004} Most rodox-flow bateres are plagued by the cross- ‘over of active materials. This erostover leads o decreased ‘ell effcieney and eycle life. Previous attempis by others in the fied t block the crossover of aetive-species often led 10 ‘decreased membrane ionic conductivity, which reduces the rate capability ofthe cell. BRIEF DESCRIPTION OF THE DRAWINGS 10005] The foregoing aspects and others will be realy appreciated by the skilled artisan trom the following description of illustrative embodiments when read in con= junction with the accompanying drawings. 10006] FIG. illustrates series of edox-active oligomers (RAOs),a vielogen monomer (12), viologen dimer 2a), 2 Viologen trimer Ga) an acylpyridinium trimer (3b), and a DBS trimer (3c). [0007] FIG. 2 illwintes an average number of ACN ‘molecules a a funetion of distance from the molecule’s Vin der Waals surface. [0008] FIG. 3A illustrates an equivalent concentration (C,,)the concentration of ROM that would be observed with 10 jum membrane and C,-0.1 M. FIG, 3B illustrates measuring the effective difsion coefficient (Dz) of each ROM through different membranes 10009] FIG. 4 illustrates that both aa. aeylpyridinium trimer (3b) and a DB3 trimer (3e) were blocked by eross- Finked PIM-1 membranes, with Sh diffusing through the membrane slower than the lower limit of quantification of 38x10" can? "and 3e diffusing through the membrane ‘with Dyg(8-120.7)x10"" em? 55 [0010] "FIG. & ilustrates a viologen monomer (La) at 26 state of charge and optimal configurations ofits HOMO and LUMO orbitals, Nov. 30, 2017 011] FIG, 6 illustrates a viologen dimer (2a) at 4+ state fof charge and optimal configurations of its HOMO and LUMO orbitals [0012] FIG. 7 ilustates a viologen trimer (3a) at 6 tate fof charge and optimal configurations of its HOMO and LUMO orbitals. LUMO, LUMO", and LUMO"? are nearly degenerate, [0013] FIG. 8 illustrates fre energy profile for la! The collective variable isthe distance between centers of masses of ROM and Py. Coy 0-1 M [0014] FIG. 9 illustrates a ree energy profiles for la'=*™* se. The collective variable is the distance between centers of masses of ROM and ACN. Cgoy70.1 M [0015] FIG, 10 ittutrates eyeic voltammetry ofa) 1a, b) 2a, ) 38, d) 35, and e) Se. Alleyele voltammograms Were collected with a 1 mm glassy carbon working electrode and Pr wire counterelectrode, All potentials are given vs. Ag/Aa". The sean rate was 100 mV’ s“!. All CVs were ‘acquired with T mM ROM ia 0.1 M LiPP, in aeetonitele (e-), 0. M TBAPF, in propylene carbonate (d), or 0.1 M ‘TRAPF, in dimethoxyethaae (e). [0016] FIG. 11 ilosteates eaibeation plots for ) viologen ‘monomer (1a), 6) viologen dimer (2a), ¢) viologen trimer Ga), ) acylpyridinium trimer (3b), and e) DBS trimer (3c). The black and red lines correspond to the low and high ceoncentration calibration regimes, respectively [0017] FIG. 12lustrates measured concentration of ROM in the pemeste compartment asa function of time (points) ‘nd finear fis (ines) for a) viologen monomer (Ia). b) viologen dimer Qa), ¢) viologen trimer Ga), ) aeypyri- eevtlyte (eed to as anolyte or catholyte, depending oa Dia! Rade the identity of the molseles). During the operation ofthe Selim) SW =ODHIDE GoeyaIS oye TRARY sTorage device, catholyte and anolyte soltions are RWB) RETEST SLI SBT flowed past (or through) cureat collectors that serve asthe positive and negative electrode, respectively As the batery ‘discharged or charged, the roe active oligomers change TABLE 5 Sasa Dy inn? ral sn HOM al ‘Cosine ete ave FINE Mt ‘Volga aed ROM a AOS Mosome(la)G4e0Hx 107 03.202) «104 1 eo.) «10% Bacay Gtrogeiet espe SR Moms Tiers) G2F0H 4107 Ga ens Io Rao Avaya RAO incr (89) G7 03) 107 = tr 207) 10 Tino ta ge or og wo eg ie ha pr ig ABLE 6 Dinetins al volume of the ober at none ta cals tea of I, 2 tt ong wh te cad Sint asi par sage ab nal set 2) Shite Soke Ent ie he know spe an sen Molit ster "Sober asic ean Woline Hone Day Blots Ba Scie thy Go TAS Meare” “caret Deer) 438 1828 Gata Loto’ Lae tos TABLE 7 iti mnie fr BS “ices Qu QulF Ry ims Newnes umd ay” el teh Cane Tigao sn 07 ae 28 oe 2 ubeioe sabe? 6am 040 tines enon iva Pet on 10054] FIG. 16 ilustrates a representative flow-cellsche- ‘mati fr redox-law batteries employing oligomeric organic ‘active materials (RAOs) and size-selective microporous oxidation state, and counterions flow through a selective ‘membrane to complete the eieuit. [0086] The selective membrane in various embodiments consists of sizeselective porous polymer membranes with pores small enough to block crossover of the oligomeric active material while stil allowing transport of supporting jons in the electrolyte. Various embodiments are character ined by the use of both: 1) Redox-active oligomeric organic molecules and 2) sizeselective membranes that lock the crossover of (1) and allow the mavement of supporting ions in solution, [0057] By combining redox-aetive oligomers with size- selective membranes, we were able to solve a nimber of ‘outstanding problems in the field of energy storage. Most redox-flow bateries are plagued by the erossover of active ‘materials. This crossover leads to decreased cel ficiency and eyele life. Previous attempts by others in the Held 10 block the erossover of active-species often led to decreased ‘membrane ionic conductivity, which reduces the rate eapa- bility ofthe cell [0088] In another strategy for blocking active-species crossover, the use of lage, polymerie change storage mol- ‘ecules results in improved crossover performance without sacrificing fonie conductivity, but at the cost of increased Solution viscosity and decreased electron transfer Kinetics. ‘This inereases the pumping losses in redox-flow batteries [0059] However, various embodiments provide the best of both approaches while circumventing their limitations: 1) [By using small (eative © polymers) molecules, the soht- tion viscosity and electron transfer Kinetics can be kept low ‘and fast, respectively; 2) By pairing redox-oetive oligomersUS 2017/0346104 Al with sizeselective membranes, the crossover of active: species can be greatly reduced without dramatically sacei- fcing ionic conduetvity. Thus, various embodiments allow for energy storage devices with longer eyele life, higher cellcieney, and better rate capability 10060] A number of technical challenges wore overcome ‘while developing this invention. Firs, the design and syn= thesis of suitable redox-active oligomeric molecules pre- sented a challenge. Not all ralox-ative oligomeric mol- ‘ecules exhibit reversible electrochemistry aad long-term, stability in all oxidation state, so we worked to find several ‘examples of molecules that fit the requirements of energy storage devices. Second, we overcame a number of chal- Jenges related to the preparation and modification of mem- brane materials. By incorporating crosslinking. and other post-synthotc modifications, we were able to tune the pore- size of the selective membranes in onder to contol theie active-species blocking and fon tansport ability, [0061] AlL-Onanic redox-flow batteries are well posi- tioned to offer low-cost, multichour elestrochemical energy storage at large seale in line with targets for grid modern- ization, During low-battery operation, solutions of redox- active organic molecules (ROMS) in electrolyte are circu Tated through the negative and positive elecrode ‘compartnents of an electrochemical cell, These compat ments are electronically isoluted from each otber by un jon-iansporting membrane separator. In onder to maximize cyle-life and efficiency, itis imperative to block ROMS fiom migrating between electrode compartments during ‘yeling while also maintsining facile transpor ofthe work ing ion. In working on this subject mater, we were hoping to develop active-materials and. membranes that, when paired together, would result in docreasod active-materal ‘crossover with minimal impact to cell kinetics or membrane ‘conductivity. Ponent electrodes paired with ceramic membranes, which fare expensive and dificult 0 seale; 2) thick macroporous separators paired with mixed-clectrode formulations (2. anolyte and catholyte present in both electrode compart ments), which lead to coulombie and voltage inefficiencies: ‘and 3) mesoporous separators paired W mers (RAPS), which can be dificult to pump through ‘electeochemieal eel at high molecular weight and at all, States-o-change. Our strategy to implement ROM oligomer ization, as opposed to polymerization, should also serve (© relain facile charge trinsfer kinetics otherwise characteristic ‘of ROM monomers, which are essential for power quality fand high active-mterial utilization, 10063] _ Various embodiments are expected to have appli- ations in multi-hour power delivery as befits such a device Jor grid-scale energy storage. In addition, various embod ments could find use for renewable energy storage in resi ‘dental, commercial, and. indus buildings. Various ‘embodiments could also be wseful for backupredundant power for eritical infrastructure of for use in locations with poor grid reliability. With respect tothe later, i an be wsed fas the energy storage device for nano and mierogsids, powering offgrid communities, isolated island communi ties, construction sites, mines, ete. redoxaetive poly Nov. 30, 2017 {0064] Various embodiments describe @ redox flow cell comprising at Icast one redox active organic molecule {ROM or redox active oligomer (RAO), an elecuolyte, nd ‘niroporous membrane {0068} redox flow cell wherein the undiluted RAO is a lig {0066} redox flow cell wherein the united RAO is an sonic compound. {0067| A redox Now cll wherein the RAO is a monodis- petse chemical compound comprising atleast two redox Jective omic molecules, chosen fem nitoxide radials, nivonslnivonie radials, thal racals, thifulvalenes, ‘betes hola, tiophenes,viologens.teaketopipers ines, quinxalins, wirylamines, ciarybikslamins, qh ones, authoquinones, meuilloencs,carbazles, Noalky- Jnted 4-aeylpyrdinioms, alkylated 4-benzoylyridiniums, 1 asithonst-2 Sal Tbenzenes, 12.5(dalkylaminoyy- clopropeniuns, beazofarazans, henzothidiazoes, nirobon- ‘enc, and isomers and drivaives thre and chemical Scaffoll to which the redox active organie molecules are covalently” Bound, chosen from aliphatic hydrocarbons, {eli aliphatic hydrocarbons, aromatic hydrocarbons, poly jolie aromatic hydrocarbons, alkylene glyeols, alkglene Jnines, quatemay alkylene minis, aliphatic esters, ao sabe eters, aliphatic eles, aromatic ethers aliphatic hio- ethers, aromatic thjoethers, aliphatic amides, aromatic unies, alpha sulfoes, aromate slfones, and combina tions and derivatives thereat [0068] A redox flow cell wherein the RAO is poydis- petse chemical compound comprising atleast twa redox fetive omatic molecules, chosen fom nitoxide radial, ‘ivonylnitoxie radials, tial roils, hiafuvalenes ‘ote, thiolams, thiophene, viologens.teraketopipe ‘nes, guinoxalines,warlamines,cayetkylamines, ones, anthraquinones, metallsenes,caebazoles, Nak) Inte -scylpyrdinioms, Nealkylted4-benzayipyriinions Asithoxst-2Sialklbenzenes, 1,2%-dialkylaminoyy- clopropeniums,beazofuravans, benzoihadivols, itoben- ‘ones, and isomers al derivatives thereof and 2 chemical lfld to whieh the redox active organic molecules re covalently bound, chosen from aliphatic hydrocarbons {ei aliphatic bydrocarbons, aromatic hydrocarbons, poly elie aromatic hydrocarbons, alkylene glycols, alkene mines, quatemay allen iminiums, lipatc estes, ao rat esters, aliphatic ees, aromatic ethers aliphatic thio- ethers, aromatic thjoeters, alipltic amides, arom mds, aliphati sulfone, arom slfones and combina- tions and derivatives therol {0069} A. chemical sclfold to which the redox active fommanie molecules are covalently bound to form & RAO, is Tinea. {0070} A chemical scllold 10 which the redox aesive cmmanie molecules are covalently bound to form # RAO, is branched {007H] A chemical seatfold to whieh the redox aetive organic molacules are covalently Bound 1 form 8 RAO. is eel [0072] A ox flow cll wherein the ROM or RAO isan Janie compound and sed united, ce a8 solution di persion, oF suspension in Water oF an rpc solvent [0073] | A redox ow cell wherein the ROM oF RAO is sed 2s soktion, dispersion, or suepension in an aqueous or an craic electoyteUS 2017/0346104 Al Wl 10074] A redox flow ell wherein the electrolyte is ‘aqueous or organic solution containing at least one dissolve sal, 10075] A redox flow cell wherein the microporous mem- brane comprises: a polymer of intrinsic. microporosity (PIM), a thermally-rearranged polymer (TR polymer), & metal-organie framework (MOF), a covalent organic frame- work (COF), a carbon molecular sieve (CMS), a porous ‘coordination polymer (PCP), a microporous 2-limensional material or atomic layer, or few-layer stacks of one or more Iypes oF microporous 2-dimensional materials or atomic layers. 10076] A redox flow cell wherein the microporous mem brane is chemically crosslinked 10077] A redox flow cell wherein the microporous mem- brane comprises « composite containing at least one of the following: a polymer of intrinsic mieroporosty (PIM), & thermally-rearranged polymer (TR polymer), a metalor ganic framework (MOF), a covalent organic framework (COP), a carhon molecular sieve (CMS), porous coordi nation polymer (PCP), microporous 2-dimensional mate- rial or atomic layer, or few-layer stacks of one or more types ‘of microporous 2-dimensional materials or atomic layers. [0078] A redox flow cell wherein the microporous mem- brane is an unsupported membrane (5 t0 500 microns ia thickness), 10079] A redox flow cell wherein the microporous mem - brane is a supported microporous selective layer (0.5 to 500 microns in thickness) comprised of selective layer, chosen from a polymer of intrinsic microporosity (PIM). a ther- mally-rearanged polymer CIR polymer), a metal-organic framework (MOF), a covalent organic framework (COF), & ‘carbon molecular sieve (CMS), a porous coordination poly mer (PCP). a microporous 2-limensional material or atomic layer, or few-layer stacks of one or more types of micropo- ous 2-dimensional materials or atomic layers; of, a chemi cally crosslinked selective aver incorporating 2 polymer of intrinsic microporosty (PIM), thermally-rearranged poly- mer (TR polymer), @ metal-organic lramework (MOF), 3 ‘covalent orgenie framework (COP), a carbon molecule sieve (CMS), a porous coordination polymer (PCP), microporous 2-dimensional material of atomic layer, oF Tew-layer slacks of one or more types of microporous 2-dimensional materials of atomic layers; oF, a composite Selective layer, incorporating atleast one polymer of int ‘ie microporosity (PIM), dhermally-rearraiged polymer (TR polymer), metal-organic framework (MOF), covalent ‘organic Famework (COF), carbon molecular sieve (CMS), porous coordination polymer (PCP), microporous 2-dimen- sonal material or atomic layer, or few-layer stacks of one oF sore types of microporous” 2-dimensional materials or mic layers; and where the support is either porous ‘organic oF porous inorganic support: andl where the support js coated on a single side or on both sides with the same selective layer of with two different selective layers of the same thickness or of dilferent thickness (0.5 t $00 microns in thickness) [0080] A redox flow cell wherein the microporous mem- brane reduces the diffsive permeability and rate of cross- ‘over of the ROM or RAO Between the electrode compart mien inthe redox flow cell Nov. 30, 2017 [0081] redox flow cell wherein the miictoporous mem brane blocks the dilsive permeability and crossover of the ROM or RAO between the electrode compartments in the redox How cell ‘What is claimed is 1. A redox flow cell comprising at east one redox active organie molecule (ROM) or redox active oligomer (RAO); an electolyte; and 4 microporous membrane 2. The redox flow cell of claim 1 wherein the undiluted RAO is a lig 3. The redox How cell of claim 1 wherein the undiluted RAO js an onic compound. 4. The redox flow cell oF claim 1 wherein the RAO is 2 ‘monodisperse chemical compound comprising: atleast wo redox active organic molecules, chosen from nitroxide ra cals, nitronylnitroxide radicals, thiazyl radical, tiafulva- Tenes, thioether, thiolanes,thiophenes, viologens. ttrake- topiperazines, uinoxalins, Teiarylamines, Gurylalkylamines, quinones, ambrauinones, metallocenes, carbazoles, Nelkylated 4-oeylpyridiniams, Nealkylated ‘-benzoyipyridiniums, 1,4-dialkoxyl-2,5-alkylbenzenes, 1.2.3-(alkylamino eyclopropeniums, benzofurazans, ben- rothiaiszoes, nitrobenzenes, and isomers and derivatives thereof; and a chemical seaffo to which the redox active ‘onganie molecules are covalently bound, chosen from al phatic hydrocarbons, cyclic aliphatic hydrocarbons, aro- ‘matic hydrocarbons, polyeyelie aromatic hydrocarbons, alkylene glycols, alkylene imines, quatomary alkylene imi niums, aliphatic esters, aromatic esters, aliphatic ethers, aromatic ethers, aliphatic thioether, i thioether, Aliphatic amides, aromatic amides, aliphatic sulfones,aro- ‘matic sullones, and combinations and derivatives thereof '5. The redox flow cell of claim 1 wherein the RAO is 2 polydisperse chemical compound comprising: at last two redox active orzanie molecules, chosen from nitroxide radi cals, nitonylnitride radicals thiazy] radical, thialulva- Jenes, thioether, thiolanes,thiophenes, viologens, tetrake- topiperazines, ‘quinoxalines, ‘eiarylamines, iarylalkylamines, quinones, anthraquinones, metallocenes, carbazoles, Nealkylted 4-2eylpyridiniums, N-alkylated ‘:benzoyipyridiniams, _1,4dialkoxyl-2,5-dalkylbenzenes, 1.234ialkylamino)eyclopropeniums, benzofurazans, ben othiodiazoes, nitrobenzenes, and isomers and derivatives thereol; and a chemical scaffold to which the redox active ‘organic molecules are covalently bound, chosen from al phatic hydrocarbons, cyclic aliphatic hydroesebons, aro- hydrocarbons, polyeyctic aromatic hydrocarbons, alkylene glycols, alkylene imines, quatemary’ alkylene in fitins, aliphatic esters, aromatic esters, aliphatic ethers, Aromatic ethers, aliphatic thioethers, aromatic thioethers, aliphatic amides, aromatic amides, aliphatic sulfones, aro- nate sulfones, and combinations and derivatives there 6. The chemical scaffold in claim 4 or claim Sto which the redax active organic molocules are covalently bound %9 form 2 RAO, is liner. 17. The chemical scaffold in claim 4 or claim 5, to which the redox active omzanie molecules are covalently bound 10 form 2 RAO, is branched 8. The chemical scaffold ia claim 4 or claim to whieh the redox active omganic molecules are covalently hound t0 orm RAO, is eylicUS 2017/0346104 Al 9. The redox flow cell of elaim 1 wherein the ROM oF RAO is an ionic compound and wsed undiluted, oF as @ solution, dispersion, or suspension in water of an organie solvent 10, The reiox low coll of claim f wherein the ROM oF RAO is used as a solution, dispersion, or suspension in an ‘aqueous or an organic electrolyte, IL, The redox flo cell of claim 1 wherein the electrolyte js an aqueous oF organic solution containing, at least one dissolved salt 12. The redox flow cell of elaim 1 wherein the micropo- rous membrane comprises: a polymer of iatrinsie micropo- rosity (PIM), athermally-rearranged polymer (TR polymer) 2 metal-organic framework (MOF), a covalent organic framework (COF), a carbon molecular sieve (CMS), porous coordination polymer (PCP), a microporous 2d mensional material or atomic layer, or few-layer stacks of ‘one or more types of mieroporois 2-dimensional materials ‘or atomic layers 13, The redox flow cell of elaim 7 wherein the micropo- rous membrane is chemically ersslinked. 14, The redox fl cell of elaim 1 wherein the micropo- rous membrane comprises « composite containing at last ‘one of the following: a polymer of intrinsic microporosty (PIN), a thermally-rearranged polymer (TR polymer), & ‘metal-organic framework (MOF), a covalent organic frame- ‘work (COF), a carbon molecular sieve (CMS), 9 porous ‘coordination polymer (PCP), a microporous 2limensional ‘material or atomic layer, o¢few-laver stacks of one or more Iypes of microporous 2-dimensional materials or atomic layers. 15, The redox flow cell of elaim 1 wherein the micropo- ous membrane is an unsupported membrane (5 10 500 microns ia thickness) 16. The redox flow cell of claim 1 wherein the micropo- rous membrane is a supported microporous selective layer (0 to 500 microns in thickness) comprised of: a selective Nov. 30, 2017 layer, chosen from a polymer of intinsie microporosity (PIM), a thermally-eatranged polymer (TR polymer), a ‘metal-organie framework (MOF), a covalent organic frame- ‘work (COF}, a carbon molecular sieve (CMS), ports ‘coordination polymer (PCP), a microporous 2-dimensional ‘mateeal or atomie layer, of few-ayer stacks of one or more types of microporois 2-dimensional materials or atomic layers; or, a chemically crosslinked selective layer incorpe ring a polymer of intrinsic microporosity (PIM), a ther ‘mally-rearanged polymer (TR polymer) & metal-organic framework (MOF), a covalent organic framework (COP), a carbon molecular sieve (CMS), a porous coordination pol mer (PCP), a mieroporous 2-dimensional material o atom layer, or few-layer stacks of one or more types of micropa ruts 2imensional materials o atomic layers; of, a com- posite selective layer, incorporating a least one polymer of intrinsic mieroporosty (PIM), thermally-rearranged poly- mer (TR polymer), metal-organic framework (MOF), eova- Tent omni framework (COF), carbon molecular sieve (CMS), porous coordination polymer (PCP), microporous 2dimensional material a atomic layer, oF few-ayer stacks ‘of one or more types of mieroporsis 2-dimensional mate- Fials or atomic layers; and where the support is either a Poros omganie oF porous inorganic support: and where the support i coated on single side or on both sides with the samme selective layer or with two different selective layers of the same thickness oF of different thickness (0.5 10 500 microns in thickness). 17. The redox flow cell of claim 1 wherein the micropo- rus membrane reduces the diffusive permeability and rate fof erossover of the ROM or RAO between the electrode ‘compartments inthe redox fw cell 18, The redox flow cell of claim 1 wherein the micropo- ous membrane blocks the difusive permeability ad cross- over of the ROM or RAO between the electrode compart- sient in the redox Now cell