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Article

Hydrogen Release and Uptake of MgH2 Modified by Ti3CN MXene

by
Xiantun Huang
1,†,
Chenglin Lu
2,†,
Yun Li
3,*,
Haimei Tang
2,
Xingqing Duan
2,
Kuikui Wang
4 and
Haizhen Liu
2,5,*
1
Department of Materials Science and Engineering, Baise University, Baise 533000, China
2
Guangxi Novel Battery Materials Research Center of Engineering Technology, Guangxi Colleges and Universities Key Laboratory of Blue Energy and Systems Integration, School of Physical Science and Technology, Guangxi University, Nanning 530004, China
3
School of Mechanical and Electrical Engineering, Quzhou College of Technology, Quzhou 324000, China
4
College of Materials Science and Engineering, Qingdao University, Qingdao 266071, China
5
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China
*
Authors to whom correspondence should be addressed.
†
These authors contribute equally to this work.
Inorganics 2023, 11(6), 243; https://doi.org/10.3390/inorganics11060243
Submission received: 29 April 2023 / Revised: 27 May 2023 / Accepted: 2 June 2023 / Published: 5 June 2023
(This article belongs to the Special Issue State-of-the-Art and Progress in Metal-Hydrogen Systems)
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Versions Notes

Abstract

:
MgH2 has a high hydrogen content of 7.6 wt% and possesses good reversibility under normal conditions. However, pristine MgH2 requires a high temperature above 300 °C to release hydrogen, with very slow kinetics. In this work, we utilized Ti3CN MXene to reduce the operating temperature and enhance the kinetics of MgH2. The initial temperature of MgH2 decomposition can be lowered from 322 °C for pristine MgH2 to 214 °C through the employment of Ti3CN. The desorbed MgH2 + 7.5 wt% Ti3CN can start absorption at room temperature, while the desorbed pristine MgH2 can only start absorption at 120 °C. The employment of Ti3CN can significantly improve the hydrogen release kinetics of MgH2, with the desorption activation energy decreasing from 121 to 80 kJ mol−1. Regarding thermodynamics, the desorption enthalpy changes of MgH2 and MgH2 + 7.5 wt% Ti3CN were 79.3 and 78.8 kJ mol−1, respectively. This indicates that the employment of Ti3CN does not alter the thermal stability of MgH2. Phase evolution studies through the use of X-ray diffraction and electron diffraction both confirm that Ti3CN remains stable during the hydrogen release and uptake process of the composite. This work will help understand the impact of a transition metal carbonitride on the hydrogen storage of MgH2.

1. Introduction

Hydrogen energy is acknowledged as an ideal strategy to solve energy shortages and environmental pollution issues. However, hydrogen under ambient conditions is a gas of low density (0.089 kg m−3) [1]. In addition, it is flammable and combustible with a wide explosion limit of 4−75 vol%. Therefore, the safe and compact storage of hydrogen is an important issue when utilizing hydrogen energy on a large scale [2,3,4].
Solid-state hydrogen storage, with the hydrogen bonded in a hydrogen storage material, is a good method to store hydrogen since it has a very large capacity (>50 kg m−3). In addition, the method is safe since it can be operated under low hydrogen pressure (generally <5 MPa). Construction of high-performance materials for hydrogen storage is the key issue in developing a solid-state hydrogen storage system [5,6,7,8,9,10,11].
MgH2 has attracted extensive attention as a material for hydrogen storage due to its large capacity of 7.6 wt% and the ability to reversibly store hydrogen [12,13,14]. In addition, there is an abundant resource of Mg on Earth, which makes large-scale application possible. However, MgH2 with high thermal stability requires a high temperature to desorb hydrogen. Moreover, the hydrogen sorption process is very slow for MgH2 when the temperature is not high enough. These two drawbacks have severely limited the practical application of MgH2. Constructing nanoscale Mg-based materials [12,15,16,17,18,19,20], alloying Mg with other metals [8,21,22,23,24], or introducing additives [25,26,27,28,29,30,31,32,33,34,35,36,37,38] are the commonly utilized strategies to modify the hydrogen sorption properties of MgH2.
In the past decade, MXenes (transition metal carbides/nitrides with layered structures) have received much attention in catalysis, energy storage, and conversion. MXene has also been demonstrated to show the positive impact on MgH2 [35,39,40,41,42,43,44,45,46,47]. In 2016, Liu et al. [47] first reported the enhancing impact of Ti3C2 MXene on MgH2. It was shown that the employment of 7 wt% Ti3C2 can reduce the starting hydrogen desorption temperature of MgH2 to 180 °C. Li et al. [44] used Ti2C MXene to reduce the temperature of MgH2 by 37 °C. It was suggested that the Ti elements with multivalences will enhance the electron transfer during hydrogen sorption. Lu et al. [31] showed that V2C MXene can tailor both the kinetics and thermodynamics of MgH2. Liu et al. [40] demonstrated that the hybrid of Ti3C2 and V2C MXenes exhibits a synergistic impact on MgH2. The starting temperature of the hydrogen release of MgH2−Ti3C2/V2C can be reduced by 140 °C. Bimetallic MXene which contains two transition metals also has a good enhancing impact on MgH2. For example, Shen et al. [46] reported that MgH2 + 10 wt% (Ti0.5V0.5)3C2 can start desorption at 196 °C. Wang et al. [42] displayed that NbTiC MXene reduces the starting hydrogen desorption temperature of MgH2 to 195 °C. It has been supposed by many researchers that the unique layered structures and the active transition metals contained within both contribute to the enhanced hydrogen storage properties of MgH2 [40,42,43,44,46,47].
Based on the above introduction, MXene materials have shown excellent enhancing influence on MgH2. However, the studies mainly focus on carbides. The impact of transition metal nitrides or carbonitrides on MgH2 is not clear currently. In this work, we first synthesized a layered transition metal carbonitride (Ti3CN MXene) and then used it to modify the hydrogen sorption properties of MgH2. The hydrogen release and uptake kinetics and thermodynamics of MgH2 modified by Ti3CN MXene will be investigated. Microstructures will be studied to reveal the role of Ti3CN MXene in modifying MgH2.

2. Results

Ti3CN MXene was synthesized by the exfoliation of Ti3AlCN MAX (hexagonal layered transition metal carbides and nitrides). A hydrofluoric acid solution was used to remove the Al layers from Ti3AlCN to synthesize the layered Ti3CN MXene. Figure 1a shows the XRD spectrum of Ti3AlCN MAX and Ti3CN MXene. The diffraction peak of the (002) crystalline plane shifting to a lower angle indicates the exfoliation of Ti3AlCN MAX to form the layered Ti3CN MXene. The SEM picture in Figure 1b indicates that Ti3CN MXene has a layered structure. In Figure 1c, the elemental mappings show that the Ti, C, and N elements are all distributed uniformly in the material. Some traces of the Al element were also observed in the material. The above characterizations indicate the successful synthesis of the layered Ti3CN MXene.
The Ti3CN MXene was mixed with MgH2 by ball milling to obtain MgH2 + m wt% Ti3CN (m = 0, 5, 7.5, 10) composites. Figure 2a shows the hydrogen release curves of the MgH2 + m wt% Ti3CN (m = 0, 5, 7.5, 10) composites when the temperature was increased from room temperature (RT) to about 400 °C at 2 °C min−1. The as-milled MgH2 without additive starts desorbing hydrogen at 322 °C and could offer a capacity of 7.0 wt% when the temperature reached 400 °C. Excitingly, the addition of Ti3CN can significantly lower the starting temperature of MgH2 desorption to 214 °C. This means a reduction of 108 °C in the starting temperature. The 7.5 wt% Ti3CN-doped MgH2 has a slightly lower hydrogen desorption temperature than the 5 wt% Ti3CN-doped MgH2. However, further increasing the Ti3CN content to 10 wt% does not further reduce the temperature of MgH2 but will slightly reduce the capacity of the composite. Considering achieving both low temperature and high capacity, the MgH2 with the addition of 7.5 wt% of Ti3CN was selected for further absorption studies. Figure 2b shows the hydrogen absorption curves of the desorbed MgH2 + 7.5 wt% Ti3CN composite and the pristine MgH2 at 4 MPa H2. During absorption, the temperature was increased from RT to 400 °C at 2 °C min−1. The desorbed MgH2 starts to absorb hydrogen at about 120 °C and could absorb 7.4 wt% H2 after the temperature was ramped to 400 °C. It is exciting that the desorbed MgH2 + 7.5 wt% Ti3CN sample can start to absorb hydrogen at RT and absorb 7.0 wt% H2 at 400 °C. Therefore, Ti3CN MXene can significantly improve the non-isothermal hydrogen desorption and absorption performance of MgH2.
The hydrogen release kinetics of MgH2 and MgH2 + 7.5 wt% Ti3CN were studied by testing the isothermal hydrogen desorption curves, as shown in Figure 3a,d, respectively. The MgH2 without an additive can achieve fast kinetics only at a temperature higher than 350 °C. However, the MgH2 + 7.5 wt% Ti3CN composite has fast hydrogen desorption kinetics even at a lower temperature below 300 °C. At a constant temperature of 300 °C, MgH2 + 7.5 wt% Ti3CN can desorb 6.6 wt% H2 within 10 min and 6.9 wt% within 60 min. Therefore, the hydrogen release kinetics were greatly improved by Ti3CN addition. The curves in Figure 3a,d were further studied by the Johnson–Mehl–Avrami (JMA) equation and the Arrhenius equation. The JMA equation is:
ln[−ln(1 − α)] = nlnk + nlnt,
where α refers to the extent of the reaction; n represents the Avrami index; t is the time; k stands for the reaction rate constant. The isothermal hydrogen desorption curves were converted to JMA plots (ln[−ln(1 − α)] vs. lnt) as shown in Figure 3b,e. Then, linear fitting was performed to obtain the n and nlnk from the slopes and the intercepts. The lnk values were then plotted vs. 1000/T based on the Arrhenius equation, which is:
lnk = −Ea/RT + lnA,
where Ea refers to the activation energy; R represents the universal gas constant; and A stands for a constant. The Arrhenius plots (lnk vs. 1000/T) are shown in Figure 3c,f. Then, linear fitting was performed to obtain the values of Ea from the slope. The desorption activation energy for MgH2 + 7.5 wt% Ti3CN was estimated to be 80 kJ mol−1, which is much lower compared to MgH2 without an additive (121 kJ mol−1). This indicates that Ti3CN improved the hydrogen release kinetics of MgH2.
The thermodynamics of MgH2 were further studied by testing the pressure–concentration isotherms (PCT) and using the van’t Hoff equation written as:
ln(p/p0) = −∆H/RT + ∆S/R,
where p refers to the plateau hydrogen pressure; p0 stands for the standard atmosphere pressure; ∆H represents the enthalpy change of the reaction; and ∆S represents the entropy changes of the reaction. Figure 4a,c shows the hydrogen desorption PCT curves of the two samples at various temperatures. From the PCT curves, the plateau hydrogen pressures (p) can be obtained. Then, the van’t Hoff plots (ln(p/p0) vs. 1000/RT) can be made (Figure 4b,d). The slopes of the linear fitting lines give the values of ∆H. The enthalpy change for the hydrogen release reaction of MgH2 + 7.5 wt% Ti3CN was estimated to be 78.8 kJ mol−1, which is very equal to that of MgH2 without an additive (79.3 kJ mol−1). Therefore, Ti3CN addition does not alter the thermodynamics of MgH2.
To reveal the role of Ti3CN MXene in tailoring the hydrogen storage of MgH2, the structures of MgH2 + 7.5 wt% Ti3CN in different states were studied by X-ray diffraction (XRD). Figure 5b−d shows the XRD profiles of MgH2 + 7.5 wt% Ti3CN at different stages, with the as-synthesized Ti3CN MXene for reference (Figure 5a). After ball milling (Figure 5b), MgH2 and Ti3CN were observed in the sample, suggesting that it is a physical mixture of the starting materials. After hydrogen desorption (Figure 5c), MgH2 decomposes and Mg forms. Ti3CN is still observed in the desorbed sample, which indicates that Ti3CN does not react with other components and stays stable in the sample. It should be noted that MgO is observed in the sample, which may be due to the partial oxidation of MgH2/Mg during sample transfer or testing. After hydrogen absorption (Figure 5d), MgH2 is fully recovered and Ti3CN is still observed in the sample. From the above structure evolution studies, it can be seen that Ti3CN stays stable during the hydrogen release and uptake process. Therefore, Ti3CN mainly plays the role of an efficient catalyst for the hydrogen release and uptake of MgH2. This is consistent with the results in Figure 4 in that the thermodynamics of MgH2 is not altered by the addition of Ti3CN.
The microstructures of the MgH2 + 7.5 wt% Ti3CN composite after rehydrogenation were further studied by SEM, TEM, EDS, and SAED methods. Figure 6a shows the SEM image of the composite, which displays that the particles of the composite are of several microns. Figure 6b shows the EDS elemental mappings of the composite. The Mg, Ti, C, and N elements are all distributed very uniformly in the composite. Figure 6c shows the TEM image of the composite with its SAED pattern shown in Figure 6d. In the SAED pattern, MgH2, Mg, and Ti3CN are observed. These three components are also observed in the HRTEM images in Figure 6e−i. The presence of Ti3CN is consistent with the XRD results in Figure 5d, which again suggests that Ti3CN mainly plays the role of an efficient catalyst for MgH2. It is interesting that Mg is detected in the rehydrogenated composite, which is different from Figure 5d. In Figure 5d, Mg is not observed in the XRD pattern. This indicates that the high-energy electron beam may have stimulated the partial decomposition of the Ti3CN-modified MgH2. It should be also noted that only those MgH2 particles that are contacting with Ti3CN can be stimulated to decompose by the high-energy electron beam, as shown in regions 1 and 3 of Figure 6e. In region 4 of Figure 6e, MgH2 without contacting with Ti3CN is not decomposed. Therefore, Ti3CN indeed is an excellent catalyst for MgH2.

3. Discussion

From the above results, it can be said that Ti3CN MXene can greatly enhance the hydrogen sorption kinetics of MgH2. The addition of Ti3CN can lower the initial hydrogen release temperature of MgH2 from 322 °C to 214 °C, with a reduction of 108 °C. Moreover, the desorbed MgH2 starts to absorb hydrogen at about 120 °C, while the desorbed MgH2 + 7.5 wt% Ti3CN sample can start to absorb hydrogen at RT. The MgH2 + 7.5 wt% Ti3CN has a desorption activation energy of 80 kJ mol−1, which is significantly lower than that of pristine MgH2 (121 kJ mol−1).
However, it seems that Ti3CN does not alter the thermodynamics of MgH2. Many published papers have demonstrated that MXene materials such as Ti3C2 [41,45,47], Ti2C [44], NbTiC [42], (Ti0.5V0.5)3C2 [46], etc., can enhance the hydrogen sorption kinetics of MgH2. However, there is barely any work that has reported that MXene materials can reduce the thermal stability of MgH2 except for V2C MXene [31]. Therefore, it can be deduced that most MXene materials do not change the thermodynamics of MgH2 but mainly alter the kinetics of MgH2.

4. Materials and Methods

Ti3AlCN MAX (500 mesh, 98% purity) was purchased from Laizhou Kaixi Ceramic Co., Ltd., Laizhou, China. MgH2 (98% purity) was purchased from Langfang Beide Commerce and Trade Co., Ltd., Langfang, China. HF (analytical purity, 40%) was purchased from Aladdin, Shanghai, China. These reagents were used as received without any further treatment.
HF-etching was used to synthesize the layered Ti3CN MXene. In the experiment, 3 g of Ti3AlCN MAX was added into a 40 mL HF solution with a concentration of 40%. The solution was then stirred at 30 °C for 18 h followed by centrifugation three times. The rotation speed used for centrifugation was 3500 rpm. After that, the sediment was washed until the pH value of the deionized water used was higher than 6. Then, the sediment was dried in a freeze-dryer for 24 h. After that, Ti3CN MXene can finally be obtained.
Ti3CN was then mixed with MgH2 by ball milling under an argon atmosphere to prepare MgH2 + m wt% Ti3CN (m = 0, 5, 7.5, 10) samples at a planetary ball mill (Pulverisette 7, Fritsch, Germany). The as-received MgH2 and the as-synthesized Ti3CN were first weighted based on the compositions in a glove box filled with high-purity argon and then placed in a milling jar. Some milling balls were also placed in the milling jar with a ball-to-powder ratio of 40:1. After sealing, the milling jar was transferred to the planetary ball mill. All samples were milled at 400 rpm for 10 h.
An X-ray diffraction (XRD) instrument (Miniflex 600, Rigaku, Japan) was utilized to determine the phase structures. The incident ray was Cu Kα radiation and the scanning speed was 2 °C min−1. A working current of 200 mA and a working voltage of 40 kV were used during the tests. The samples for the XRD test were sealed with transparent tape to prevent the samples from oxidizing during the sample transfer and test. Scanning electron microscopy (SEM, JSM-6510A, JEOL, Japan) was employed to analyze the morphologies. The samples were adhered to conductive tape. The transfer of the samples was carried out carefully to protect the samples from contacting the air. An attached X-ray energy dispersive detector (EDS) was employed to collect the elemental distributions. A transition electronic microscope (TEM, Tecnai G2 F20, FEI, The Netherlands) with a voltage of 200 kV was used to study the microstructures of the samples. Anhydrous acetone was used to disperse the sample on Cu grids.
A Sievert-type apparatus built by the Institute of Metallic Materials, Zhejiang University, Hangzhou, China, was utilized to study the hydrogen release and uptake behavior of the samples. During the non-isothermal hydrogen release tests, the samples were heated gradually from RT to 400 °C at 2 °C min−1 from an initial pressure of 10−4 MPa. During the non-isothermal hydrogen uptake tests, the temperature program was the same as the isothermal hydrogen release test. At the starting point of the heating program, hydrogen of 6 MPa was charged into the sample holder. During the isothermal hydrogen release tests, the samples were first heated to the target temperature with a hydrogen back pressure of 6 MPa. When the temperature was stabilized, hydrogen gas was rapidly vented to start hydrogen desorption. An automatic Sievert-type apparatus (IMI-Flow, Hiden, UK) was used to collect the PCT curves of the samples.

5. Conclusions

Layered Ti3CN MXene was successfully synthesized by exfoliation of Ti3AlCN MAX with HF as the etching solution. The layered Ti3CN can significantly improve the kinetics of MgH2. In particular, MgH2 + 7.5 wt% Ti3CN shows good hydrogen desorption performance, with an initial hydrogen release temperature of 214 °C and a low hydrogen release reaction activation energy of 80 kJ mol−1. Moreover, the desorbed MgH2 + 7.5 wt% Ti3CN can absorb hydrogen at RT, while the desorbed pristine MgH2 can only start absorption at 120 °C. The layered Ti3CN barely changes the thermodynamics of MgH2 since the enthalpy changes of the hydrogen release reactions of MgH2 and MgH2 + 7.5 wt% Ti3CN are very close (79.3 and 78.8 kJ mol−1, respectively). Ti3CN stays stable during the hydrogen release and uptake process of the MgH2−Ti3CN composite, which means that Ti3CN mainly plays the role of an efficient catalyst for MgH2. This work confirms that transition metal carbonitrides also have a good catalytic impact on the hydrogen release and uptake properties of MgH2.

Author Contributions

Conceptualization, C.L. and X.H.; methodology, X.D.; validation, H.T.; formal analysis, C.L.; investigation, X.H.; writing—original draft preparation, H.L.; writing—review and editing, Y.L. and K.W.; supervision, H.L.; project administration, H.L.; funding acquisition, Y.L., K.W. and H.L. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Science and Technology Department of Guangxi Zhuang Autonomous Region, grant number GuiKeAD21238022, the National Natural Science Foundation of China, grant number 52001079, the Quzhou Science and Technology Project, grant number 2022K103, and the open foundation of State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, Guangxi University, grant number 2022GXYSOF16.

Data Availability Statement

The data presented in this study are available from the corresponding author upon request.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. (a) XRD spectrum of Ti3AlCN and Ti3CN. (b) SEM image of Ti3CN. (c) EDS elemental distributions of Ti3CN.
Figure 1. (a) XRD spectrum of Ti3AlCN and Ti3CN. (b) SEM image of Ti3CN. (c) EDS elemental distributions of Ti3CN.
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Figure 2. (a) Hydrogen release curves of MgH2 + m wt% Ti3CN (m = 0, 5, 7.5, 10) with the temperature rising from RT to 400 °C at 2 °C min−1. (b) Hydrogen uptake curves of MgH2 and MgH2 + 7.5 wt% Ti3CN at 6 MPa H2 with the same temperature program as (a).
Figure 2. (a) Hydrogen release curves of MgH2 + m wt% Ti3CN (m = 0, 5, 7.5, 10) with the temperature rising from RT to 400 °C at 2 °C min−1. (b) Hydrogen uptake curves of MgH2 and MgH2 + 7.5 wt% Ti3CN at 6 MPa H2 with the same temperature program as (a).
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Figure 3. Hydrogen release curves at various temperatures (a,d), JMA plots (b,e), and Arrhenius plots (c,f) of MgH2 without addition (upper) and MgH2 + 7.5 wt% Ti3CN (down).
Figure 3. Hydrogen release curves at various temperatures (a,d), JMA plots (b,e), and Arrhenius plots (c,f) of MgH2 without addition (upper) and MgH2 + 7.5 wt% Ti3CN (down).
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Figure 4. Hydrogen desorption PCT curves (a,c) and van’t Hoff plots (b,d) of MgH2 without addition (upper) and MgH2 + 7.5 wt% Ti3CN (down).
Figure 4. Hydrogen desorption PCT curves (a,c) and van’t Hoff plots (b,d) of MgH2 without addition (upper) and MgH2 + 7.5 wt% Ti3CN (down).
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Figure 5. XRD profiles of Ti3CN MXene (a) and MgH2 + 7.5 wt% Ti3CN after ball milling (b), after hydrogen desorption (c), and after hydrogen absorption (d).
Figure 5. XRD profiles of Ti3CN MXene (a) and MgH2 + 7.5 wt% Ti3CN after ball milling (b), after hydrogen desorption (c), and after hydrogen absorption (d).
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Figure 6. SEM image (a), EDS elemental mappings (b), TEM image (c), SAED pattern (d), and HRTEM image (e–i) of the MgH2 + 7.5 wt% Ti3CN composite after rehydrogenation.
Figure 6. SEM image (a), EDS elemental mappings (b), TEM image (c), SAED pattern (d), and HRTEM image (e–i) of the MgH2 + 7.5 wt% Ti3CN composite after rehydrogenation.
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MDPI and ACS Style

Huang, X.; Lu, C.; Li, Y.; Tang, H.; Duan, X.; Wang, K.; Liu, H. Hydrogen Release and Uptake of MgH2 Modified by Ti3CN MXene. Inorganics 2023, 11, 243. https://doi.org/10.3390/inorganics11060243

AMA Style

Huang X, Lu C, Li Y, Tang H, Duan X, Wang K, Liu H. Hydrogen Release and Uptake of MgH2 Modified by Ti3CN MXene. Inorganics. 2023; 11(6):243. https://doi.org/10.3390/inorganics11060243

Chicago/Turabian Style

Huang, Xiantun, Chenglin Lu, Yun Li, Haimei Tang, Xingqing Duan, Kuikui Wang, and Haizhen Liu. 2023. "Hydrogen Release and Uptake of MgH2 Modified by Ti3CN MXene" Inorganics 11, no. 6: 243. https://doi.org/10.3390/inorganics11060243

APA Style

Huang, X., Lu, C., Li, Y., Tang, H., Duan, X., Wang, K., & Liu, H. (2023). Hydrogen Release and Uptake of MgH2 Modified by Ti3CN MXene. Inorganics, 11(6), 243. https://doi.org/10.3390/inorganics11060243

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