Ion-vacancy coupled charge transfer model for ion transport in concentrated solutions
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摘要
We present a conceptual framework for understanding and formulating ion transport in concentrated solutions, which pictures the ion transport as an ion-vacancy coupled charge transfer reaction. A key element in this picture is that the transport of an ion from an occupied to unoccupied site involves a transition state which exerts double volume exclusion. An ab initio random walk model is proposed to describe this process. Subsequent coarse-graining results in a continuum formula as a function of chemical potentials of the constituents, which are further derived from a lattice-gas model. The subtlety here is that what has been taken to be the chemical potential of the ion in the past is actually that of the ion-vacancy couple. By aid of this new concept, the driving force of ion transport is essentially the chemical affinity of the ion-vacancy coupled charge transfer reaction, which is a useful concept to unify transport and reaction, two fundamental processes in electrochemistry. This phenomenological model is parameterized for a specific material by the aid of first-principles calculations. Moreover, its extension to multiple-component systems is discussed.
We present a conceptual framework for understanding and formulating ion transport in concentrated solutions, which pictures the ion transport as an ion-vacancy coupled charge transfer reaction. A key element in this picture is that the transport of an ion from an occupied to unoccupied site involves a transition state which exerts double volume exclusion. An ab initio random walk model is proposed to describe this process. Subsequent coarse-graining results in a continuum formula as a function of chemical potentials of the constituents, which are further derived from a lattice-gas model. The subtlety here is that what has been taken to be the chemical potential of the ion in the past is actually that of the ion-vacancy couple. By aid of this new concept, the driving force of ion transport is essentially the chemical affinity of the ion-vacancy coupled charge transfer reaction, which is a useful concept to unify transport and reaction, two fundamental processes in electrochemistry. This phenomenological model is parameterized for a specific material by the aid of first-principles calculations. Moreover, its extension to multiple-component systems is discussed.
We present a conceptual framework for understanding and formulating ion transport in concentrated solutions, which pictures the ion transport as an ion-vacancy coupled charge transfer reaction. A key element in this picture is that the transport of an ion from an occupied to unoccupied site involves a transition state which exerts double volume exclusion. An ab initio random walk model is proposed to describe this process. Subsequent coarse-graining results in a continuum formula as a function of chemical potentials of the constituents, which are further derived from a lattice-gas model. The subtlety here is that what has been taken to be the chemical potential of the ion in the past is actually that of the ion-vacancy couple. By aid of this new concept, the driving force of ion transport is essentially the chemical affinity of the ion-vacancy coupled charge transfer reaction, which is a useful concept to unify transport and reaction, two fundamental processes in electrochemistry. This phenomenological model is parameterized for a specific material by the aid of first-principles calculations. Moreover, its extension to multiple-component systems is discussed.
引文
1 Richey FW,Dyatkin B,Gogotsi Y,Elabd YA.J Am Chem Soc,2013,135:12818-12826
2 Simon P,Gogotsi Y.Acc Chem Res,2013,46:1094-1103
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13 Gadzuric S,Suh C,Gaune-Escard M,Rajan K.Metall Mat Trans A,2006,37:3411-3414
14 Zhao Y,Daemen LL.J Am Chem Soc,2012,134:15042-15047
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16 Fan L,Wei S,Li S,Li Q,Lu Y.Adv Energy Mater,2018,8:1702657
17 Cogswell DA,Bazant MZ.Nano Lett,2013,13:3036-3041
18 Malik R,Zhou F,Ceder G.Nat Mater,2011,10:587-590
19 Suo L,Borodin O,Gao T,Olguin M,Ho J,Fan X,Luo C,Wang C,Xu K.Science,2015,350:938-943
20 Kilic MS,Bazant MZ,Ajdari A.Phys Rev E,2007,75:021503
21 Zhao H.Phys Rev E,2001,84:051504
22 Bazant MZ,Kilic MS,Storey BD,Ajdari A.Adv Colloid Interface Sci,2009,152:48-88
23 Kornyshev AA.J Phys Chem B,2007,111:5545-5557
24 Borukhov I,Andelman D,Orland H.Phys Rev Lett,1997,79:435-438
25 Wang H,Thiele A,Pilon L.J Phys Chem C,2013,117:18286-18297
26 Ferguson TR,Bazant MZ.J Electrochem Soc,2012,159:A1967-A1985
27 Lee AA,Kondrat S,Vella D,Goriely A.Phys Rev Lett,2015,115:106101
28 Bikerman JJ.London Edinburgh Dublin Philos Mag J Sci,1942,33:384-397
29 Riess I,Maier J.Phys Rev Lett,2008,100:20590
30 Cahn JW,Hilliard JE.J Chem Phys,1958,28:258-267
31 Braga MH,Ferreira JA,Stockhausen V,Oliveira JE,El-Azab A.JMater Chem A,2014,2:5470-5480
32 Ravikumar B,Mynam M,Rai B.J Phys Chem C,2018,122:8173-8181
33 Maldonado-Manso P,Losilla ER,Martínez-Lara M,Aranda MAG,Bruque S,Mouahid FE,Zahir M.Chem Mater,2003,15:1879-1885
34 Fu J.J Am Ceram Soc,1997,80:1901-1903
35 Zhang Y,Zhao Y,Chen C.Phys Rev B,2013,87:134303
36 Abbott AP,Harris RC,Ryder KS.J Phys Chem B,2007,111:4910-4913
37 Zhou F,Cococcioni M,Marianetti CA,Morgan D,Ceder G.Phys Rev B,2004,70:235121
38 Morgan D,van der ven A,Ceder G.Electrochem Solid-State Lett,2004,7:A30
39 Sun Y,Lu X,Xiao R,Li H,Huang X.Chem Mater,2012,24:4693-4703
40 Islam MS,Driscoll DJ,Fisher CAJ,Slater PR.Chem Mater,2005,17:5085-5092
41 Leonardi E,Angeli C.J Phys Chem B,2010,114:151-164
42 Krishna R,Wesselingh JA.Chem Eng Sci,1997,52:861-911
43 Krishna R,van Baten JM.Chem Eng Sci,2009,64:3159-3178
44 Lee AA,Kondrat S,Oshanin G,A Kornyshev A.Nanotechnology,2014,25:315401
2 Simon P,Gogotsi Y.Acc Chem Res,2013,46:1094-1103
3 Lee AA,Kondrat S,Kornyshev AA.Phys Rev Lett,2014,113:048701
4 Kornyshev AA,Spohr E,Vorotyntsev MA.Electrochemical Interfaces:At the Border line.New York:Wiley,2002
5 Bockris JO,Reddy AKN,Gamboa-Aldeco ME.Modern electrochemistry 2A.2nd Ed.New York:Kluwer Academic Publishers,2002
6 Lee AA,Colby RH,Kornyshev AA.Soft Matter,2013,9:3767-3776
7 Lu W,Fadeev AG,Qi B,Smela E,Mattes BR,Ding J,Spinks GM,Mazurkiewicz J,Zhou D,Wallace GG,MacFarlane DR,Forsyth SA,Forsyth M.Science,2002,297:983-987
8 Baughman RH,Cui C,Zakhidov AA,Iqbal Z,Barisci JN,Spinks GM,Wallace GG,Mazzoldi A,de Rossi D,Rinzler AG,Jaschinski O,Roth S,Kertesz M.Science,1999,284:1340-1344
9 Wang X,Mehandzhiyski AY,Arstad B,Van Aken KL,Mathis TS,Gallegos A,Tian Z,Ren D,Sheridan E,Grimes BA,Jiang DE,Wu J,Gogotsi Y,Chen D.J Am Chem Soc,2017,139:18681-18687
10 Fedorov MV,Kornyshev AA.Chem Rev,2014,114:2978-3036
11 Van Aken KL,Beidaghi M,Gogotsi Y.Angew Chem Int Ed,2015,54:4806-4809
12 Giordani V,Tozier D,Tan H,Burke CM,Gallant BM,Uddin J,Greer JR,McCloskey BD,Chase GV,Addison D.J Am Chem Soc,2016,138:2656-2663
13 Gadzuric S,Suh C,Gaune-Escard M,Rajan K.Metall Mat Trans A,2006,37:3411-3414
14 Zhao Y,Daemen LL.J Am Chem Soc,2012,134:15042-15047
15 Liu Z,Fu W,Payzant EA,Yu X,Wu Z,Dudney NJ,Kiggans J,Hong K,Rondinone AJ,Liang C.J Am Chem Soc,2013,135:975-978
16 Fan L,Wei S,Li S,Li Q,Lu Y.Adv Energy Mater,2018,8:1702657
17 Cogswell DA,Bazant MZ.Nano Lett,2013,13:3036-3041
18 Malik R,Zhou F,Ceder G.Nat Mater,2011,10:587-590
19 Suo L,Borodin O,Gao T,Olguin M,Ho J,Fan X,Luo C,Wang C,Xu K.Science,2015,350:938-943
20 Kilic MS,Bazant MZ,Ajdari A.Phys Rev E,2007,75:021503
21 Zhao H.Phys Rev E,2001,84:051504
22 Bazant MZ,Kilic MS,Storey BD,Ajdari A.Adv Colloid Interface Sci,2009,152:48-88
23 Kornyshev AA.J Phys Chem B,2007,111:5545-5557
24 Borukhov I,Andelman D,Orland H.Phys Rev Lett,1997,79:435-438
25 Wang H,Thiele A,Pilon L.J Phys Chem C,2013,117:18286-18297
26 Ferguson TR,Bazant MZ.J Electrochem Soc,2012,159:A1967-A1985
27 Lee AA,Kondrat S,Vella D,Goriely A.Phys Rev Lett,2015,115:106101
28 Bikerman JJ.London Edinburgh Dublin Philos Mag J Sci,1942,33:384-397
29 Riess I,Maier J.Phys Rev Lett,2008,100:20590
30 Cahn JW,Hilliard JE.J Chem Phys,1958,28:258-267
31 Braga MH,Ferreira JA,Stockhausen V,Oliveira JE,El-Azab A.JMater Chem A,2014,2:5470-5480
32 Ravikumar B,Mynam M,Rai B.J Phys Chem C,2018,122:8173-8181
33 Maldonado-Manso P,Losilla ER,Martínez-Lara M,Aranda MAG,Bruque S,Mouahid FE,Zahir M.Chem Mater,2003,15:1879-1885
34 Fu J.J Am Ceram Soc,1997,80:1901-1903
35 Zhang Y,Zhao Y,Chen C.Phys Rev B,2013,87:134303
36 Abbott AP,Harris RC,Ryder KS.J Phys Chem B,2007,111:4910-4913
37 Zhou F,Cococcioni M,Marianetti CA,Morgan D,Ceder G.Phys Rev B,2004,70:235121
38 Morgan D,van der ven A,Ceder G.Electrochem Solid-State Lett,2004,7:A30
39 Sun Y,Lu X,Xiao R,Li H,Huang X.Chem Mater,2012,24:4693-4703
40 Islam MS,Driscoll DJ,Fisher CAJ,Slater PR.Chem Mater,2005,17:5085-5092
41 Leonardi E,Angeli C.J Phys Chem B,2010,114:151-164
42 Krishna R,Wesselingh JA.Chem Eng Sci,1997,52:861-911
43 Krishna R,van Baten JM.Chem Eng Sci,2009,64:3159-3178
44 Lee AA,Kondrat S,Oshanin G,A Kornyshev A.Nanotechnology,2014,25:315401