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Feb 11, 2015 - *E-mail: [email protected]. Cite this:J. Phys. Chem. Lett. 6, 5 ... Energy densities of Li ion batteries, limited by the capacities of cathode materials, must increase by a factor of 2 or more to give all-electric automobiles a 300
Feb 11, 2015 - Prospects and Limits of Energy Storage in Batteries. K. M. Abraham*. Department of Chemistry and Chemical Biology, Northeastern University Center for Renewable Energy Technology, Northeastern. University, Boston, Massachusetts 02115, U
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Perspective
Stretchable Aqueous Batteries: Progress and Prospects Woo-Jin Song, Sangyeop Lee, Gyujin Song, and Soojin Park ACS Energy Lett., Just Accepted Manuscript • DOI: 10.1021/acsenergylett.8b02053 • Publication Date (Web): 28 Nov 2018 Downloaded from http://pubs.acs.org on December 1, 2018
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Stretchable Aqueous Batteries: Progress and Prospects Woo-Jin Song, Sangyeop Lee, Gyujin Song and Soojin Park*
Dr. W.-J. Song, S. Lee, S. Park* Department of Chemistry, Division of Advanced Materials Science Pohang University of Science and Technology 77 Cheongam-ro, Nam-gu, Pohang 37673, Republic of Korea
G. Song Department of Energy Engineering, School of Energy & Chemical Engineering Ulsan National Institute of Science and Technology (UNIST) Eonyang-eup, Ulju-gun, Ulsan 44919, Republic of Korea
The development of stretchable electronics is indispensable for realizing next-generation wearable devices, such as sensors, health care devices, and electronic skin. A key challenge for achieving complete and independent wearable devices is to develop stretchable power sources. This issue should be addressed appropriately before the realization of wearable devices. Very recently, stretchable aqueous rechargeable batteries as power supplies have received much attention for wearable devices owing to their intrinsic safety and high-power density. In this perspective, we present the current status and the latest advances in researches on stretchable aqueous batteries, especially aqueous Li-ion batteries and zinc-based ones. Also, we briefly provide the design of stretchable materials and battery systems for stretchable aqueous batteries. Further, an overview of general technical issues confronting their development is presented, and a brief discussion on the future outlook of this field is provided.
The development of stretchable electronics has generated tremendous interest in research community and industry.1 As direct applications of stretchable electronics, wearable electronic devices will cause the paradigm shift in consumer electronics such as smart electronic skin, artificial organs, and continuous health monitoring.2,3 A key challenging issue for designing complete and independent wearable electronic devices is to develop stretchable power sources that can maintain electrochemical performance during repeated deformations such as folding, twisting, and even stretching.4 Among various power sources, supercapacitors based on non-faradaic reaction are also typically regarded as promising wearable energy-storage devices.5-11 However, they are not appropriate for the use in power source for independent portable wearable devices due to their relatively low energy density compared to batteries that can store energy electrochemically through faradaic reactions.12 Normally, Li-ion batteries (LIBs) provides great potential as stretchable power sources for wearable devices owing to their design flexibility, high energy density, and long cycle life.13 However, non-aqueous electrolyte inside LIBs is inherently flammable and volatile. Especially for stretchable batteries, thermal runaway can easily occur because of internal short circuit caused by external deformations, which leads to battery fire and explosion (Figure 1a).14 In particular, this safety issue is a prerequisite for stretchable batteries because of the nature of wearable devices that are implanted in human body or contacted with human skin. Furthermore, the sensitivity to ambient atmospheres increases battery cost because of the requirement of a strictly dry environment.15 These limitations encourage us to explore alternative battery chemistry with high safety and low cost for wearable energy-storage devices.
An aqueous rechargeable battery is one of the most ideal candidates as wearable energy-storage devices because aqueous electrolyte possesses intrinsic safety and high ionic conductivity (two orders of magnitude higher than that of non-aqueous electrolyte) (Figure 1b).16-18 In addition, aqueous electrolytes are environment friendly and cost-efficient for manufacture. In this regard, aqueous batteries are considered as promising wearable energy-storage devices. Recently, various stretchable aqueous batteries based on alkali metal-ion batteries (e.g., Li and Na) and metal-ion ones (e.g., Mg, Al, and Zn) have been intensively studied by designing innovative battery architectures to achieve desirable deformability and reliable electrochemical performance. In this perspective, we provide a short summary of recent progress in stretchable aqueous batteries, especially in both aqueous Zn-based batteries and aqueous Li-ion ones. Further, we briefly introduce stretchable materials and battery design for stretchable aqueous batteries. It is worth noting that there are many excellent review articles of materials and fundamental research on stretchable batteries.19-21 Herein, we aim to cover the state-of-the-art achievements of stretchable aqueous batteries for wearable electronics. Finally, we discuss the summary and future outlook of this emerging field.
Generally, conventional aqueous batteries are typically composed of rigid components such as electrodes (e.g., cathode and anode), a separator membrane, and packaging materials. However, such rigid batteries cannot keep their functional performance under various mechanical deformations. To realize stretchable batteries, each rigid component of batteries should be replaced with a stretchable one
(Figure 2). As a core component of batteries, a stretchable electrode has been fabricated using various strategies such as wave structures,22-24 origami,25,26 and polymer composites.27 Typically, gel electrolytes composed of a polymeric network having an aqueous electrolyte have been widely used in stretchable batteries. And those not only play a role of a separator membrane but also serve as an ionic conductor.28 Poly(vinyl alcohol) (PVA) is widely employed owing to its high ionic conductivity and excellent mechanical property. Moreover, from the viewpoint of battery structures, new architectures to achieve stretchable batteries have been demonstrated as well, such as self-similar serpentine geometries and cable-type structures.29–31 In the following section, recent important advances in stretchable aqueous batteries based on the aforementioned various battery designs are introduced, including one- and twodimensional configurations (Table 1).
Stretchable Aqueous Zinc-based Batteries Zn-based batteries among various metal-ion batteries, including Zn-air, Zn-MnO2, Zn-Ni, and Zn-Ag, have aroused extensive interest in both battery and electronics societies, because Zn metal features high abundance, high theoretical specific capacity (820 mA h g−1), and low electrochemical potential in aqueous media (−0.76 V vs. standard hydrogen electrode (SHE)). Zn-based batteries, thus, are considered as the promising battery chemistry for wearable energy-storage devices.32,33 Battery design to integrate into wearable devices is important depending on application purposes. Normally, stretchable Zn-based battery design can be categorized into one-dimensional (i.e., cable-type) and two-dimensional structures (i.e., planar layout). In two-dimensional structures, coplanar design where electrodes are placed on the same plane enables ultrathin batteries and can possess high power density
owing to high ionic conductivity.34 For example, Gaikwad and coworkers proposed a stretchable ZnMnO2 battery with the coplanar configuration using a silver fabric as a stretchable current collector and a mechanical support simultaneously (Figure 3a).35 This battery demonstrates an output voltage of 1.5 V and an areal capacity of 3.87 mA h cm−2. Although this battery can well maintain its electrochemical performance even under 100% strain, it is not rechargeable. Recently, rechargeable aqueous Zn-MnO2 batteries based on optimized electrolyte were reported,36,37 and their results will be introduced later. As one of the most practical power sources, Zn-Ag batteries have attracted attention owing to their unique features in terms of high power density, high specific energy density, high safety, and low selfdischarge rate.38 For this reason, they have also been widely used as practical power sources.39 As a demonstration of wearable energy-storage devices, Yan and coworkers designed stretchable rechargeable Zn-Ag batteries based on a polymer composite comprising silver nanowires (AgNWs) and polydimethylsiloxane elastomer that simultaneously acted as a stretchable current collector and cathode materials (Figure 3b).40 A stretchable anode was made by electroplating on the as-prepared polymer composite. Figure 3c shows that the stretchable full batteries assembled with both stretchable cathode and anode demonstrate analogous output voltage of ~1.63 V at a current density of 1 mA cm−2 under 80% strain, corresponding to an energy density of 0.44 mW h cm−2. Additionally, they exhibited superior cycle life without losing their electrochemical performance after 1000 cycles at both initial strain and 80% strain. Another approach to fabricate batteries with the coplanar layout is to use a printing technology including ink-jet printing and screen printing. Such printing technology is an attractive fabrication
process owing to its advantages, i.e., it is simple, cost-effective, and scalable.41 For example, epidermal Zn-Ag tattoo batteries that can be easily worn by human skin to power wearable devices was demonstrated using a screen printing process.42 The tattoo batteries revealed a stable output voltage of 1.5 V during repeated bending and stretching cycles. Recently, Kumar et al. reported all-printed stretchable Zn-Ag batteries having reversible capacity and favorable mechanical strength using printing technologies (Figure 3d).43 They introduced poly(styrene-b-isoprene-b-styrene) (SIS) block-copolymer as a high elastic binder to prevent the delamination between active materials and the current collector when the batteries were stretched, which increased the stretchability. Figure 3e shows that the output voltage of 1.11 V at a strain of 100% can be obtained, indicating the good electrochemical stability under strain. In addition, a discharge capacity was stable up to 30 cycles even under 100% strain (Figure 3f). These results demonstrated the great potential for all printed stretchable Zn-Ag batteries as power sources for wearable devices. One-dimensional batteries, including cable, yarn, and fiber type, are considered as the feasible battery configuration for wearable energy-storage devices because such architectures can be easily integrated with commercial textile and wearable devices.44,45 For example, stretchable cable-type Zn-air batteries exhibited a voltage plateau of 1.0 V at a current density of 1 A g−1 for 30 cycles and retained the electrochemical performance well under a strain of 10% (Figure 4a-c).46 Furthermore, stretchable allsolid-sate fiber Al-air batteries with a high energy density of 1168 W h g-1 and stable the electrochemical performance under 30% strain was developed.47 However, such batteries cannot achieve practical performance because of their poor cyclability and low mechanical properties. Zamarayeva and coworkers recently designed flexible and stretchable rechargeable Zn-Ag batteries using two similar geometries such as serpentine (uniaxial stretching) and self-serpentine structures (biaxial stretching) as
shown in Figure 4d.48 Especially, the resulting serpentine batteries can be stretched up to 100% strain for 500 stretching cycles without sacrificing their electrochemical performance (Figure 4e). Furthermore, they demonstrated that the cable Zn-Ag batteries can be integrated with a photovoltaic module as an energy harvesting device (Figure 4f and g). These results proposed highly stretchable cable Zn-Ag batteries having high electrochemical performance and excellent deformability by simply adjusting battery geometries. However, the stretchable batteries with serpentine architectures have considerably low energy densities and complicated fabrication procedures. Recently, to realize more effective stretchable one-dimensional Zn-based batteries, Li and coworkers demonstrated the fabrication and electrochemical performance of stretchable yarn Zn-MnO2 batteries that consisted of yarn electrodes and a novel polyacrylamide (PAM) hydrogel electrolyte as shown in Figure 4h.49 Such batteries presented outstanding mechanical properties (3000% strain) and high ionic conductivity (17.3 × 10−3 S cm−1). Remarkably, the assembled yarn Zn-MnO2 batteries with PAM electrolyte containing 2 M ZnSO4 and 0.1 M MnSO4 possessed greatly improved capacity retention of 98.5% at a current density of 2 A g−1 over 500 cycles. This PAM electrolyte played a key role in improving reaction kinetics and reducing the interfacial resistance between the electrolyte and electrodes during cycles. Good cycle performance, thus, was manifested. Even under 300% strain, the batteries showed exceptional capacity retention of 94.8% after 100 cycles as well (Figure 4i). They also demonstrated good tailorability and high energy density (53.8 mW h cm−3) as well as outstanding waterproof capability in water without noticeable electrochemical performance decay (96.5% capacity retention after 12 h soaking). Further, the authors successfully demonstrated that the yarn batteries integrated with a flexible electroluminescent panel (Figure 4j) can reveal a great potential for practical wearable devices. In addition, stretchable Mg batteries based on the wavy configuration sustained their electrochemical performance under 30% strain after 2000 stretching cycles.50
Stretchable Aqueous LIBs In 1994, Dahn and coworkers designed aqueous rechargeable lithium-ion batteries (ARLBs) comprising a LiMn2O4 (LMO) cathode and a VO2 (B) anode to replace flammable and toxic non-aqueous electrolyte with safe and natural aqueous one.51 However, the first demonstration of ARLBs showed low capacity and poor cyclability, which is difficult to be applied in practical applications. To address these drawbacks, considerable efforts have been devoted to investigating novel active materials and electrolyte chemistry.52,53 As a result, ARLB battery systems have attracted great attention for use in grid energy storage systems as well as wearable energy-storage devices owing to their safety as well as high power and energy density.54 For example, fiber-shaped ARLBs with high power density (10.22 kW kg−1 or 2.98 W cm−3) and high energy density (48.89 W h kg−1) were proposed by Zhang et al. for wearable
energy-storage
devices.55
The
batteries
exhibited
stable
electrochemical
performance under various deformations such as bending, folding, and twisting. Additionally, Zhao and coworkers demonstrated that self-healing flexible ARLBs can deliver a high energy density of 32.04 W h kg−1 and maintain their cycling performance over 200 cycles at a bending
angle of 60°.56 Although these flexible ARLBs demonstrate high energy density and reasonable flexibility, they are difficult to be applied in wearable devices because of the limitation in mechanical deformability.57
Recently, our group firstly reported stretchable ARLBs with the coplanar layout as shown in Figure 5a.58 The battery was based on a hybrid carbon polymer (HCP) composite containing multidimensional conductive fillers. The HCP composite exhibited outstanding electrical conductivity (normalized resistance, R/Ro, was 1.4 even under 200% strain) owing to synergistic effects of multidimensional fillers. Synthesized LMO and polyimide were used as active materials for cathode and anode, respectively. The assembled batteries with the aqueous electrolyte of 1 M Li2SO4, without a separator membrane, showed stable cycling performance (93% capacity retention after 500 cycles) and high rate capability (specific capacity of 65 mA h g−1 even at a rate of 60 C). They also demonstrated a stable relative capacity of 70% at a strain of 100%. Interestingly, after recovery to the initial state, the capacity of our batteries was almost recovered to the initial value (Figure 5d). Furthermore, the
stretchable full batteries connected in series steadily delivered the power to a red light-emitting diode (LED) even under 100% strain (Figure 5e), indicating that they held great promise potential as power accessories for wearable devices. However, the battery having a coplanar electrode configuration has a disadvantage in terms of volumetric energy density (W h volumecell−1) because the total volume of the coplanar layout is larger than that of the sandwich-type layout as shown in Figure 6a and b.
As mentioned in the introduction, in this field, gel electrolytes have been typically served as a dual role of a separator membrane and an electrolyte. Thus, the development of stretchable separator membranes has attracted little attention. However, because of the possibility of internal short-circuit failures during physical deformations such as crumpling and stretching, the gel electrolyte may not be suitable for use in stretchable batteries. Furthermore, polymer gel electrolyte normally possesses low ionic conductivity, thereby deteriorating battery performance.59 To address the above issues, it is indispensable to achieve the presence of a stretchable separator membrane that serves as ionic transport channel and physical barrier to
prevent internal shot-circuit between two electrodes.60 Very recently, our group proposed a stretchable separator membrane based on poly(styrene-b-butadiene-b-styrene) (SBS) blockcopolymer using non-solvent induced phase separation via scalable and simple fabrication process.61 The stretchable separator membrane demonstrated high elastic properties (a uniaxial strain of 270%, a biaxial strain of 60%), appropriate wettability in electrolytes, and high porosity (Figure 6c). We assembled sandwich-structured stretchable ARLBs using the stretchable separator membrane and as-prepared stretchable HCP composite electrodes. The batteries exhibited stable cycle performance for 200 cycles and retained 85% capacity retentions after 30 cycles even under a strain of 100% (Figure 6d). Indeed, compared with the coplanar configuration without a separator membrane discussed in our earlier work,58 the sandwich-type configuration showed significantly decreased total volume of about 40%, which can be beneficial for the volumetric energy and power densities of the resulting battery layout. These results are expected to achieve reliable stretchable aqueous batteries for wearable electronic devices.
In summary, stretchable aqueous batteries are considered as good candidates for wearable energy-storage devices because of their advantages such as high-power density and highly safe features. In this perspective, we briefly introduced the recent research progress in stretchable aqueous batteries such as Zn-based batteries and ARLBs, with a focus on battery chemistry, structure design, and electrochemical performance. Despite the advanced achievement of stretchable aqueous batteries, this emerging field is still in its early stage with regard to stretchability and electrochemical performance. Figure 7 shows that significant challenges are required to achieve reliable stretchable aqueous batteries for practical applications.
First, stretchable aqueous batteries possess low energy density compared with nonaqueous electrolyte-based commercial LIBs. The energy density depends on operating voltage and specific capacities. Unfortunately, aqueous electrolyte intrinsically possesses narrow electrochemical stability window (~1.23 V), which consequently leads to low operating voltage
and energy of aqueous batteries. Extending the electrochemical window of the aqueous electrolyte is one of the key challenges. Recently, innovative concepts of extending the operating window up to about 4 V were proposed using high concentrated aqueous electrolyte (namely, “water-in-salt” and “water-in-bisalt”) that can kinetically protect side reactions such as hydrolysis.62,63 Furthermore, developing active materials with high capacity should be conducted to improve the energy density of the batteries. Zuo et al. proposed a versatile Bi2O3 electrode material with high specific capacity (~ 357 mA h g-1 at a rate of 0.72 C) and exceptional rate capability (217C, 75000 mA g-1) for various aqueous battery systems.64 These approaches, the extension of voltage window and development of high capacity materials, could provide the opportunities for increasing energy density of stretchable aqueous batteries (Figure 7a).
Second, it is highly desired that a stable cycle life of stretchable aqueous batteries is achieved under repeating mechanical deformations. With respect to an electrode, active materials can be delaminated to a current collector when deformations are applied, leading to a fast degradation of battery performance. Also, this issue limits the high loading of active
materials. Therefore, additional effort should be devoted to both evolving electrode architectures and designing elastic binders that can accommodate high deformation stress while retaining desirable electrochemical performance. Another technical approach for solving the delamination issue under deformations is to use a patterned current collector that is fabricated by various methods such as a photolithographic process.65 This method could significantly improve not only mechanical properties of current collector but also adhesion of active materials to the current collector under strain (Figure 7b).
Third, the encapsulation of stretchable batteries has recently attracted considerable attention to design various battery shapes and to integrate wearable devices. For example, packaging materials can protect the integrity of devices and guarantee stable functions under extreme mechanical deformations and harsh environmental conditions. They should require low gas and water permeability for reliable operation of stretchable batteries, because anode side can react with water and oxygen at discharge state, leading to severe degradation of the device performance.66,67 However, packaging materials attract little attention compared with other components of stretchable batteries, such as electrodes and electrolytes. Therefore,
various efforts should be devoted to developing novel packaging materials and new process technologies that meet desirable industrial requirements (Figure 7c). In addition, the use of aqueous electrolyte has brought leakage problems under physical deformations. Gel polymer electrolyte that can play dual roles of an electrolyte and separator is also promising solution to resolve the risks of leakage when subjected to a stretching strain. Furthermore, the gel electrolytes would enhance electrochemical stability to guarantee long-term cyclability and alleviate dendritic formation because negatively charged polymer network in the gel electrolyte facilitates ionic transport uniformly in the electrode/electrolyte interphase.68 For the realization of wearable electronic devices, the most important consideration is the development of a fully stretchable electronics platform with the integration of stretchable batteries to achieve completely and independently portable wearable electronics. To address the above issue, first of all, the stretchable circuit that maintain its functionality even under deformations are highly desired.69 We hope that this perspective can throw light on the rational battery architecture and materials for stretchable aqueous batteries to open up a new chapter in future wearable electronics devices.
AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] ORCID: 0000-0003-3878-6515 Notes The authors declare no competing financial interest
Biography Woo-Jin Song is a Post Doc. in the Department of Chemistry at POSTECH. He received his Ph.D. (2018) in the Department of Energy Engineering at UNIST under the supervision of Prof. S. Park. His research interests focus on the development of deformable energy-storage systems and integration of stretchable electronics.
Sangyeop Lee received his B.S degree in Energy Engineering in 2018 from UNIST. Now, he is a Ph.D. candidate in POSTECH under the supervision of Prof. S. Park. His research interest focuses on material designs for deformable energy-storage systems. Gyujin Song received his B.S degree in Energy Engineering in 2015 from the UNIST. Now he is a Ph.D. candidate in UNIST. His research interest focuses on the design of anode materials for Li-ion and next-generation batteries. Soojin Park is a professor in the Department of Chemistry at POSTECH. He leads to Polymer-based Energy Materials Lab for various energy storage applications. Among other honors, he has received the Asia Excellence (Japan, 2012), Korea Young Scientist Presidential Award (2013), and Researcher Academy Award (2017). His current research mainly focuses on deformable batteries and design of high capacity anode materials. Homepage: https://www.spark-postech.com
ACKNOWLEDGMENT This work was supported by the Center for Advanced Soft-Electronics funded by the Ministry of Science, ICT and Future Planning as Global Frontier Project (CASE-2015M3A6A5072945).
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Figure 1. (a) Non-aqueous batteries lead to fire and explosion under repeated deformation because non-aqueous electrolyte with high flammability and high volatility acts as the fuel. (b) Aqueous batteries are relatively safe.
Figure 3. (a) Schematic illustration of stretchable Zn-MnO2 batteries with coplanar configuration. Reprinted with permission from ref. 35. Copyright 2012, Wiley-VCH. (b) Photographs of stretchable Zn-Ag batteries with the coplanar configuration under 0% and 80% strains. (c) Charge–discharge curves of the stretchable Zn-Ag batteries at a current density of 1 mA cm−2 at a strain of 0% (black line) and 80% (red line). Reprinted with permission from ref. 40. Copyright 2014, Wiley-VCH. (d) Schematic shows the fabrication process of all-printed stretchable Zn-Ag batteries with the elastic binder using a screen-printing process. The operation of all-printed stretchable Zn-Ag batteries is performed under 100% strain (left) and biaxial strain (right). (e) Voltage profiles of all-printed stretchable Zn-Ag batteries at pristine and stretching states (100% strain). (f) Discharge capacity of all-printed stretchable Zn-Ag batteries as a function of cycle at a current density of 3 mA cm−2. Reprinted with permission from ref. 43. Copyright 2017, Wiley-VCH.
Figure 4. (a) Side view of the fiber-shaped Zn-air battery. (b) Photographs of a fiber-shaped Zn–air battery before and after stretching by 10%, scale bar: 1 cm. (c) Discharge curves of the
fiber-shaped Zn–air battery with a length of 10 cm at a current density of 1 A g-1 before and after stretching by 10%. Reprinted with permission from ref. 46. Copyright 2015, Wiley-VCH. (d) Schematic diagram showing the fabrication process of fiber-shaped Zn-Ag batteries. (d) A photograph of serpentine-shaped stretchable Zn-Ag batteries under 100% uniaxial strain. (f) Schematic illustration showing an organic photovoltaic module. (g) A photograph of the stretchable battery integrated with the photovoltaic. Reprinted with permission from ref. 48. Copyright 2017, American Association for the Advancement of Science. (h) Schematic illustration of fiber-shaped stretchable Zn-MnO2 batteries. (i) Capacity retention of cableshaped stretchable Zn-MnO2 batteries at a current density of 0.3 A g−1 under 300% for 300 cycles. (j) The cable batteries were connected in series to power a display under bending state. Reprinted form ref. 49
Figure 5. (a) Schematic illustration of stretchable ARLBs with coplanar configuration. (b) A photograph of a Jabuticaba tree whose morphology is similar to the percolating network of multidimensional carbon fillers. (c) TEM images of multidimensional conductive fillers such as carbon nanotubes and carbon blacks. The inset shows that carbon blacks are adhered to the surface of carbon nanotubes. (d) Relative capacity retention of stretchable ARLBs under different stretching and releasing states. (e) Photographs of an LED powered by stretchable ARLBs connected in series at 0% and 100% strains. Reprinted with permission from ref. 58. Copyright 2018, Wiley-VCH.
Figure 6. Comparison of calculated total volumes of (a) coplanar and (b) sandwich-type structures. (c) Photographs of the stretchable separator membrane based on SBS blockcopolymer under 200% strain (up) and 60% biaxial strain (down), respectively. (d) Normalized capacity as a function as cycle at 0% strain, 100% strain, and recovery. Reprinted with permission from ref. 61. Copyright 2018, Wiley-VCH.
A key challenging issue for designing complete and independent wearable electronic devices is to develop stretchable power sources that can maintain electrochemical performance during repeated deformations such as folding, twisting, and even stretching.
In this perspective, we provide a short summary of recent progress in stretchable aqueous batteries, especially in both aqueous Zn-based batteries and aqueous Li-ion ones. Further, we briefly introduce stretchable materials and battery design for stretchable aqueous batteries.