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Hydrogen Battery Using Neutralization Energy

Article  in  Nano Energy · August 2018

DOI: 10.1016/j.nanoen.2018.08.046

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

Hydrogen Battery Using Neutralization Energy

Guo-Ming Weng1,2*, Chi-Ying Vanessa Li1*, Kwong-Yu Chan1

1
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong SAR,

China
2
Department of Chemical and Environmental Engineering, Yale University, New Haven,

Connecticut 06511, USA

*
E-mail: guoming.weng@yale.edu; cyvli@hku.hk

Abstract

Low-cost, non-toxic and environment-friendly electrochemistry is highly needed for clean

energy storage technologies. Here we propose a most simple rechargeable pH differential

hydrogen battery using neutralization energy as an efficient energy storage system to utilize

renewable energy and waste acid/base. The overall battery reaction can be simplified as

⎯⎯⎯⎯
→ 2H2O. This proposed hydrogen battery can deliver a
follow: 2H+ + 2OH- ⎯⎯⎯
⎯
discharge

charge

theoretical specific energy of up to 250 Wh kg-1 and a maximum energy density of up to 355

Wh L-1, very high values among aqueous battery systems. We show adding excessive amount

of NaClO4 can lead to effective pH maintenance, higher coulombic efficiency, higher power

and more stable cyclic performance at 9 mA cm-2. This work offers new opportunities to

develop clean and high-energy battery technologies.

Keywords: Energy storage, pH differential power sources, Hydrogen batteries,

Neutralization energy, Renewable energy

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

1. Introduction

To store the clean and renewable energy from wind and solar efficiently, various chemical

energy storage techniques have been developed.[1-11] Utilizing a very simple

electrochemistry contains low-cost and safe active species (e.g. H2O, H+ and OH-) or

preferably some “electroactive wastes” can lead to a practical, safe, clean and attractive

energy storage system. By applying the concept of pH differential,[12-14] a hydrogen battery

(HB) with very simple electrochemistry can be developed and its configuration is shown in

Fig. 1a, in which hydrogen electrode in acid acts as positive electrode while the other

hydrogen electrode in base acts as negative electrode. The electrochemistry of HB is shown

in eqns. (1-3). As shown by eqn. (3), the overall battery reaction, this hydrogen battery does

not consume H2 gas but proton and hydroxide ions. In principle (Figure S1), this HB can

yield a cell voltage of 0.83 V and a specific energy of up to 250 Wh kg-1. According to eqn.

(4),[12] the cell voltage of HB is proportional to the pH difference between the acidic and

alkaline chambers. In contrast to the conventional H2-O2 fuel cell, this hydrogen battery can

also be used as an energy storage system. This is because the proposed hydrogen battery only

involves fast and reversible hydrogen oxidation and evolution reactions, while sluggish and

irreversible 4-electron oxygen reactions[15] are eliminated. In addition, extremely high

energy density (about 355 Wh L-1) could be achieved by this system since acid/base has very

high solubility in water. Fig. 1b shows the deliverable energy of HB is one of the highest

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

values among the state-of-the-art aqueous battery systems. Detailed comparison is shown in

Table S1.

⎯⎯⎯⎯
→ H2
discharge
+ve: 2H+ + 2e- ⎯⎯⎯
⎯ Eo=0.00 V (1)
charge

⎯⎯⎯⎯
→ 2H2O + 2e-
-ve: H2 + 2OH- ⎯⎯⎯
⎯
discharge
Eo=-0.83 V (2)
charge

Overall: ⎯⎯⎯⎯
→ 2H2O
2H+ + 2OH- ⎯⎯⎯
⎯
discharge
V=0.83 V (3)
charge

𝐸𝑐𝑒𝑙𝑙 = 0.059 V × ∆pH (4)

Bipolar membrane (BPM) has been used to demonstrate the feasibility of this technology,

however, it induces low power density and acidity/alkalinity (Figures. S2 and S3 and Table

S2). Therefore, more attempts are needed to improve the cell performance of HB. If a 40-fold

excess of salt solution (e.g. NaClO4 since it has extremely high solubility) is present in either

acid or base environment, the migration flux of salt ions is around 40 times higher than that

of H+ or OH- ions according to eqns. (5) and (6) at a given electrical potential gradient (i.e.,

migration flux 𝐽𝑁𝑎+ ≫ 𝐽𝐻 + and 𝐽𝐶𝑙𝑂4− ≫ 𝐽𝑂𝐻 − ). Therefore, the internal current will be

mainly carried by the migration of salt ions and leads to an alleviated crossover of acid and

base. Note: 4 mol L-1 NaClO4 is used due to the highest ionic conductivity among the tested

concentrations, see Figures. S4 and S5 and Tables S3 and S4. Moreover, the ionic

conductivity and output power of the system can be enhanced.

Diffusion: 𝐽𝑖 = −𝐷𝑖 (𝜕𝐶𝑖 /𝜕𝑥) (5)

𝑧𝐹
Migration: 𝐽𝑖 = − [( ) 𝐷𝑖 𝐶𝑖 ] (𝜕𝜑𝑖 /𝜕𝑥) (6)
𝑅𝑇

3
 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

where 𝐽𝑖 is the flux (mol cm-2 s-1), 𝐷𝑖 is the diffusion coefficient of the ion specie (cm2 s-1),

𝐶𝑖 is the concentration of the species (mol cm-3), 𝜕𝐶𝑖 /𝜕𝑥 is the concentration gradient, 𝜑𝑖

is the electrostatic potential and 𝜕𝜑𝑖 /𝜕𝑥 is the electrical potential gradient.

2. Results and discussion

2.1 Galvanostatic test of HB with different separators

Fig. 2a shows the discharge and charge characteristics of HB with salt addition using

different monopolar membranes as separators (characteristics is shown in Table S5). In Fig.

2a, higher voltage efficiency (VE, calculated with mid-point voltage) can be obtained when

using CMI-7000 (80%), compared to that of BPM (60%). This improvement is mainly

attributed to the increment in the voltage efficiency of the voltage across the CMI-7000, as

compared the red dash Vm with the black solid Vm in Fig. 2b. It is found from Figs. 2c and 2d

that [H+] and [OH-] keep deviating from the initial concentration after charge, which reveals

relatively worse performance for the HB with CMI-7000 would occur over the cycles. This

could be due to the crossover of H+/OH- ions across the membrane that induce the

acidic/alkalinity loss. In the 2nd cycle of the HB with N-117, a serious alkalinity loss (even in

the presence of excessive 4 mol L-1 NaClO4) is observed. This result indicates the N-117

cannot effectively remain the pH difference or separate H+ and OH- ions between the two

chambers, which could be due to its very high permselectivity to proton over Na+ ion, high

hydrophilicity and very small thickness which induce a serious crossover of H+ ions through

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

the N-117.

Interestingly, we found that the cell with Nafion-324 (N-324) shows a sustainable

performance in terms of constant discharge/charge voltage plateau and good retention in

Coulombic efficiency over the cycles, which can be observed from Fig. 2a. And the good pH

maintenance could be further confirmed from Figs. 2c and 2d. The cell with N-324 shows

similar VE (79%) to that with CMI-7000 (80%). Compared to N-117 and CMI-7000, N-324

has a lower hydrophilicty or higher hydrophobicity because of the PTFE reinforcement,

which leads to less crossover of H+/OH- ions. The Coulombic efficiency (CE) of these cells

can be estimated by the change in acidity and alkalinity after the respective galvonastatic test

(Figs. 2c and 2d). Based on the estimation, the average CE of the cells with BPM, CMI-7000,

N-117 and N-324 at the 1st cycle is estimated to 98%, 86%, 40% and 100%, respectively.

Therefore, the energy efficiencies (EE) of these cells with BPM, CMI-7000, N-117 and N-

324 for the first cycle are 59%, 69%, 33% and 79%, respectively. Note that these efficiencies

are calculated without considering the amount of H2 supply (5 or 20 mL min-1) during

operation, as this HB theoretically does not consume H2.

As shown in the Vm curves of Fig. 2b, the HB cell with BPM shows a very high areal

membrane resistance is 188 Ω cm2; while 33 Ω cm2, 19 Ω cm2 and 37 Ω cm2 for CMI-7000,

N-117 and N-324, respectively. This indicates using a monopolar membrane could greatly

improve the VE and EE by reducing the IR drop in the voltage across the membrane. A

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

possible ions transport across the monopolar membrane (e.g. N-324) could be proposed and

illustrated in Figures S6 and S7. The stable cell performance is mainly due to a suitable

hydrophilicity/hydrophobicity ratio for the PTFE-reinforced Nafion-324 that can block the

crossover of H+/OH- well while allow the permeation of the dominant salt ions (Na+ and

ClO4-).

2.2 Polarization curve analysis

With a given electrolyte combination, the HB with smaller inter-electrode gap (2 cm)

shows a higher discharge voltage and a lower charge voltage at a given current density than

those with larger gap (6 cm), respectively (Fig. 3a). This leads to a higher power density and

energy efficiency for the cell with 2 cm gap. It is seen from Vm in Fig. 3b, the smaller

distance for the ions transport across the membrane leads to a lower voltage across the

membrane during charge and a higher voltage across the membrane during discharge. For the

HB with BPM, high overpotential during charge and discharge is observed and this is mainly

caused by the large resistance and low-efficiency ions transport of the BPM (Figure S8). With

the same electrolytes, the system with 2 cm gap had a peak power density of 5.28 mW cm-2

(at 14.04 mA cm-2) which is higher than that of 6 cm gap (3.70 mW cm-2 at 8.64 mA cm-2)

(Fig. 3c). This value (5.28 mW cm-2) is c.a. 4.2 times higher than that with BPM (1.28 mW

cm-2). That means both improved pH maintenance and higher power output performance are

achieved by using N-324 and salt addition. In Fig. 3c, a HB with 2 cm gap and 1 M

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

HClO4/NaOH + 4 M NaClO4 shows a peak power density of 6.89 mW cm-2 at the current

density of 16.92 mA cm-2. More data on the effect of acid/base concentrations are shown in

Figures. S9, S10 and S11. We find higher acid/base concentration can lead to higher output

power and energy. Since the output power is closely related to the internal resistance of the

battery system, the relatively low power density could be further enhanced by replacing with

highly conductive membrane, shortening the inter-electrode gap, and optimizing the ratio of

acid/base to salt of the electrolyte.

2.3. Cyclic performance

Fig. 4 shows cyclic performance of HB with N-324 at different inter-electrode gaps. The

breakdown of voltage losses in the hybrid cell and performance of individual components can

be determined by examining the voltage profiles in Fig. 4 and Vcell equals to Ep-En+Vm. As

shown in Fig. 4, the discharge/charge process for these systems at 9 mA cm-2 are fairly

reversible and stable, the discharge voltage (Vcell) are able to maintain at around 0.4 V for the

system with 0.2 M HClO4/NaOH + 4 M NaClO4 and gap=6 cm (Vcell in Fig. 4a), 0.45 V for

the system with 0.2 M HClO4/NaOH + 4 M NaClO4 and gap=2 cm (Vcell in Fig. 4b). This

stability is also reflected in the curves of Ep and En with corresponding steady positive and

negative electrode reactions. The IR drop between discharge and charge of Vcell is the sum of

that of Ep, En and Vm. This voltage loss determines the VE of the HB cell. By comparing the

IR drop between discharge and charge in respective Ep, En and Vm in Figs. 4a and 4b, the

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

voltage loss across the N-324 is no longer the major contributor on the overall IR drop. This

means NaClO4 addition can greatly reduce the ionic transport resistance. The result with 1 M

HClO4/NaOH + 4 M NaClO4 and gap=2 cm at 9 mA cm-2 is shown in Figure. S12. Table S6

summarizes the changes in [H+] and [OH-] before and after the cycle test to show the long-

term cell performance of salt addition at different electrolyte combinations. These results

show the salt addition can greatly improve the cell performance of the HB. Based on the

[H+]/[OH-] changes after the cycling test (Fig. 4 and Table S6), we find that the most

optimized HB (0.2 M HClO4/NaOH + 4 M NaClO4, 2 cm) showed ~0.75% acidity/alkalinity

loss per cycle at 9 mA cm-2. This small acidity/alkalinity loss is mostly due to the undesirable

crossover of H+/OH- ions through the membrane. The stability of the system can be improved

by another highly ion-selective membrane or a tailor-made separator specific to this pH

differential rechargeable batteries. A simple approach to refill low-cost abundant acid and

base at regular intervals can be a viable alternative. Four-tanks operation mode is proposed to

achieve better cyclic performance in our future work (Figure S13). Stack design (referred to

conventional fuel cell stack[16]) with optimal flow fields (both H2 gas and liquid electrolyte)

can also be applied to achieve higher voltage and power for most applications, in which the

number of cells in a stack and the electrode area of a single cell determine voltage and output

power. In addition, further reduction in capital cost by using alternative low-cost catalysts

(e.g., Pt group metal-free catalyst)[17] is needed to make this hydrogen battery more

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

competitive against other energy storage technologies.

3. Conclusion

In summary, the key issues (acidity/alkalinity loss and low power output) were identified

for the HB with different separators. By adding excessive amount of NaClO4, dominant

migration flux of Na+ and ClO4- ions across the separator was reached and improved ions

transport across the separator was achieved. The concentrations of electrolytes, inter-

electrode gap and the other cell/operation parameters with impacts on the electrochemical

performance of the hydrogen battery were systematically investigated. The improved

hydrogen battery with N-324 (1 M HClO4/NaOH + 4 M NaClO4) demonstrates a peak power

density of 6.89 mW cm-2 at the current density of 16.92 mA cm-2. In addition, stable cyclic

performance of the improved hydrogen battery with N-324 (0.2 M HClO4/NaOH + 4 M

NaClO4) was achieved at a high current density of 9 mA cm-2. This work opens a new

direction for developing clean and high-energy battery technologies.

Acknowledgements

The work described in this paper was fully Supported by a grant from the Research Grant

Council of the Hong Kong Special Administrative Region, China (Project No.

T23-601/17-R).

Additional information

Supplementary information is available.

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

Figure 1. (a) Experimental cell arrangements of pH differential hydrogen battery with

polarity connection. (b) Comparison of the theoretical specific energy and maximum energy

density as a function of the cell voltage for hydrogen battery and state-of-the-art aqueous full-

flow batteries. The systems are Fe/Cr[9], VRF[4], AQS/Br[3], TEMPO/Viol[1],

halide/VCl3[10], sulfur/air[6], TEMPTMA/MV[5], organometallic[7], DHBQ/K4Fe(CN)6 [8]

and Mn-H[11].

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

Figure 2. a) 2-cycle discharge/charge characteristics of pH differential hydrogen battery with

different monopolar membranes at a given electrolyte combination. b) Corresponding voltage

profiles of positive electrode versus RHE1 (Ep), negative electrode versus RHE1 (En), voltage

across the N-324 (Vm). Corresponding concentration change of [H+] (c) and [OH-] (d) at each

interval to Fig. 2a.

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

Figure 3. a) Polarization curves of HB with varies electrolyte concentrations and inter-

electrode gaps. b) Corresponding voltage profiles of positive electrode vs. RHE1 (Ep),

negative electrode vs. RHE2 (En), voltage across the separator (Vm). c) Corresponding

discharge power density vs. current density curves of HB.

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 Please cite: Weng, G. M., Li, C. Y. V., & Chan, K. Y. (2018). Hydrogen battery using neutralization
energy. Nano Energy, 53, 240-244.

Figure 4. a) 10-cycle discharge/charge of HB with N-324 at 6 cm gap. b) 10-cycle

discharge/charge of HB with N-324 at 2 cm gap.

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