Materials Today Physics 20 (2021) 10058 journal homepage: ELSEVIER Materials Today Physics httpa://www.jouri ‘materials-today-physics Contents lists available at ScioncaDirect ater PHYSICS. wey Self-healable hydrogel electrolyte for dendrite-free and self-healable ® zinc-based aqueous batteries Wei Ling‘, Funian Mo **"*°, Jiaqi Wang’ Qixin Yang ‘, Yejun Qiu‘, Yan Huang" aabse, gjiang Liu *"°, Yao Liu *”*, 2 ute ey aboratory of Avance Welding and Jag, Harb Instat of Technol. Seneen, 51805, China > Reve rined Elect Tec Coner Harbin inst of Tcl Shenae, 518055, Chia * Scot of Materia Scene and Eger, Hart nite of Tecnology. Shenae, 8055, China ARTICLE INFO ABSTRACT ‘te oy ‘The poor stability of zinc anodes caused by uneven depostion|stripping ofzinc has inevitably mite the racial application of zine-based aqueous batteries (ZABs), And the self-healing property is very recessary for improved lifespan and reliability of the exible batteries under various deformations during their daily usage In this work, a new sel-healable hydrogel electrolyte (SHE) with rigi-lexible backbones is synthesized by cross-linking polymerization and composite strengthening. Owing to porous trossinking network and more hydrophilic groups, the SHE possesses hgh ionic conductivity (231 mS} and the hydrophilic groups are conductive to improve imterfacal compatibility between electrode and electrolyte, prompting much more disciplined Za metal Dlating/stripping. And the dynamic hydrogen bonds devived from the hydroxyl groups of the polymer buckbone can prompt sefshealing and stretchable property of SHES. Asa test the assembled exible ‘ine-manganese dioxide batteries delivered a high capacity of 304 mah g"at 0.5 Ag and good cyeling Stability with a capacity retention of 83.1% (vs. 625% with polyacrylamide) after 1500 charge/discharge fycls at 50 A g-+ Furthermore, the flexible bateries with SHEs can recover electrochemical pefor- Received May 2021 ecelved in revised orm june 2021 ‘ecepted 9 Jone 2021 ‘vale online 16 June 2021 ‘Zine based aqueous bates ‘Seicheatbie erogt Denaitetee growth Solhealable teres ‘mance with over 95% healing efficiency after 5 cytes of complete breaking/healing '© 2021 Eleevier Lt All rights reserve. 1. Introduction ‘With high energy density and good cycling stability, ithium ion batteries (LIBs) have governed the rechargeable battery market among consumer electronics, portable electronics and power bat- teries in the last few decades, but insufficient lithium resources, flammable organic electrolytes, and safety issues stil limit further large-scale application of LBs [1] By contrast, aqueous batteries possess high safety, environmental friendliness, low assembly cost {and high rate performance, benefiting from the usage of aqueous clectrolyte (safe reliability and high ionic conductivity) and no ‘demand of water-ree and oxygen-free conditions [8], Owing to the advantages of metalic zinc anodes (low electrochemical Potential, ~0.76 V vs, standard hydrogen electrode and high spe- ciffe capacity, 820 mAh g-! and 5855 mAh cm-*), zinc-based * correspaning autho. State Key aboratry of Advanced Welding an Joining ‘Eales: Yasboricd a (Huang) us:o.og/102016).nps202 100455 25425283)0 2021 Hsevier LA ih reserved aqueous batteries (ZABs) have been recognized as one of the most attractive candidates for next-generation high energy density Storage systems compared with other aqueous batteries [9-1] Nevertheless, the uncontrollable zine dendrite growth in liquid clectrolyte (LE), would pierce the separator and induce short- Circuiting, thus cause inferior cycling stability issues for current ZAis [12-14], So far, great efforts have been devoted to suppress zinc dendrite growth for ZABs, such as zine metal surface modifi- cation [15], 3D conductive nanostructure [6,17], nanolayer coating {18,15}, concentrated electrolytes [20,21] and hydrogel electrolytes (22,23) By turning to the hydrogel electrolytes from current LEs, the issue of zinc dendrite growth may be relieved to some extent, contributing to an improved cycling stability for ZABS [24]. In addition, the hydrogel electrolytes provide high flexibility and reliable electrochemical properties for portable and flexible elec- ‘uonics compared with LEs [25-27] Especially, when the hydrogel electrolytes have self-healing property, the flexible batteries can Stand against local stress under various deformations during theiring Fa Wag a aly usage, which an greaty prolong the fespan and reliability of| the electronic system [25-30] Recently some self-healing hydro- sg elecuolyes have been reported to be applied in the aqueous Batteries, sich a5 polyinyl alcohol (PVA) [31,32], sodium poy acrylate (PANa) [33] and. sodium polyacrylate-sodium alginate (PaNa-Ca-SA) [3], which have been achieved great progress the sell-healing property of batteries. The self-healing mechanisms can be generalized to two categories of reversible covalent bond (cycloaddition reaction, disulfide bond, acyliydrazide bond and boron-oxygen bond etc) [29.35] and dynamic non-covalent bond (tydrogen bone, onic bn, metal ligand interaction, x-7 stacking and host-uest identification ete) [36~38]}. However, many sel- healing polyelecroytes displayed poor salt solubility and insufi- cient water absorbing capacity, especialy in the mild environment, ‘which vastly restrict electrochemical performance of batteries (low ionic conductivity) and leave harmful effect (acid or alkali cond tions) on environment and human body [39]. Therefore, itis of ‘reat significance to design a kind of sl-healing polyelectrolytes ‘with excellent electrochemical performance inthe mild condition forZABs. Herein, we design a self-healable hydrogel electrolytes (SHE) with excellent stretchablty and high ion conductivity toregularize the metalic zine electrochemical behavior for flexible and mild Zs. The SHES are synthesized by cross-linking polymerization of ‘agarose molecular chain and polyacrylamide (PAM). and the car- boxymethyl cellulose (CMC) was introduced into the composite electrolytes to strengthen ther film-forming property. The greater porous crosslinking network of SHE ensures the high ionic con- uctivity 23:1 msjem at25 0) and uniform deposition of Zn metal The symmetric zinc-metal batteries with SHES can maintain a smaller voltage hysteresis (-80 mV) and be stably charged/dis- charged for upto 300 hat 5 mAlen while the batteries with LEs generated a short circuit after only less than 40 h operation, and ure PAMS showed an ever-increasing voltage hysteresis ((iom 100 mv to 200 mV) during 270 h operation. Assembled with Zn) carbon loth anode and x-Mn0, cathode, the flexible. zinc- manganese dioxide batteries delivered a high capacity of 304 mah g "ata current density f0.5 Ag. "and good eyling stability ‘with 3 capacity retention of 83.1%(120 mAh g "after 1500 charge] discharge cycles at 50 Ag. Furthermore, due to Uhe hydrogen bonding derived from abundant hydroxyl groups in the poly- cleetroyte networks, the a-MaO,{J2n battcies with the SHE can repair their electrochemical performance with over 85% healing cfciency after 5 cytes of thorough breaking/healng. 2. Results and discussions 2.1, Design ofthe sef-healable hydrogel electrolyte for dendrite-free ‘and se-healable zinc-based aqueous batteries ‘The schematic diagram of SHE with self-healing process Is shown in Fis, 1, which was fabricated by a free radical polymeri- zation of acrylamide monomers among the polymer networks of ‘agarose molecular and CMC chains, As described in the exper mental section, the agarose powder was dissolved in the deionized ‘water at high temperature (90 °C), and then acrylamide, initiator and cross-linking agent were added under cooling state. Finally, the precursor solution was gelatinized at 70°C for 24h after dissolving ‘CMC, Zn0, and MnS0q (Fig. SI). The agarose is a kind of natural plant gums that usually are used as thickening agent and coagulant, such as biological medium. Benefiting from rich hydroxyl groups, the agarose is expected to play a vital role in the selfhealing Property of SHE membrane via hydrogen-bond interaction (ig, 1b) [43,44] As a common film-forming agent, the CMC was applied to further strengthen the mechanical capacity of SHE ater ody ye 202021) 008 (Pig. $2), Compared with other metal anodes, Zn anode is able to remain a reversible deposition/stripping in aqueous electrolytes, ‘which prompt ZABs relatively high voltage platform and capacity Unfortunately like conventional lithium-ion batteries, the dendrite growth phenomenon is also liable to accur in 2ine metal anode by the influence of uneven electric feld and large current polarization, and the phenomenon with on-going may puncture the separator land result in an internal shorting failure of ZABs, As a schematic diagram displayed in Fis. c, the zinc foil is easily subjected to dendrite growth in the LE due to uneven electric field distribution land the pure PAM also not fully resolve the issue of zinc dendrite ‘growth because of poor film mechanical properties and unstable electrodejelectrolyte interface. By contrast, owing to porous crosslinking network and more hydrophilic groups, the SHE pos- sesses high jonic conductivity and excellent mechanical strength, and the hydrophilic groups are conductive to improve interfacial ‘compatibility berween electrode and electrolyte, which can effec- tivity solve dendrite growth problem through lowering the over- Potential of metal nucleation/deposition, and the risk of the lectrolyte punctured from dendrites. 22, Characterization of the sef-healable hydrogel electrolyte ‘The scanning electron microscopy (SEM) image reveals that the ‘SHE exhibits a more highly porous 3D morphology compared with PAM (Fig. 2a-f), and this structure could facilitate a higher water uptake and offer rapid ion transport pathways. In addition, it is shown that the three-dimensional cross-linking networks exist in the porous structure of SHE (Fs. 2e and 9, which may be capable of improving the mechanical strength and stretchability of gel elec= ‘uolyte.Fourier-transform infrared spectroscopy (FTIR) was applied to analyze the functional groups and bands of SHE solid electrolyte. ‘The spectra of PAM and SHE show that there are several absorption bands at 3350 em”, 2941 cm~', 1650 cm™ and 1411 m= [42]. ‘Which are attributed to N-H stretching vibration, C-H stretching vibration, C=O stretching vibration and symmetric ~COO stretching vibration, respectively (Fs. 2g). Besides, compared with PAM, the SHE possesses a stronger absorption bands at 1114 em! corresponding to hydroxyl functional groups (C-OH stretch) [45]. The abundant hydroxyl groups of the polymer backbone are conductive to the formation of hydrogen bonds in the SHE and improve the hydrophilicity of gel clectrolyte. The dynamic hydrogen bonds can prompt self-healing and stretchable property of SHES (Fig. 53), and the high hydrophilicity is helpful for enhancing ionic conductivity and interfacial compatibility of SHE solid electrolyte. To verify this point, the ionic conductivities of the PAM and SHE membranes were calculated from the AC impedance spectra via the assembly of symmetrical stainless-steli/stainless- steel batteries (Fig. 2h). According to the equation (a = SR), the ‘SHE with adding 10g agarose (PAM|CMC'1.0g agarose) possesses the highest the ionic conductivity of 23.1 mS{em at room temper- ature compared with other electrolytes (Fs. S2), which is two times higher than that of the pure PAM (11.6 mS[em). The impedance measurement of stainless-stee//SHEJstainless-steel batteries at variable temperatures is displayed in Fig. Sda, and the activation cenergy (E,) of SHE clectroiytes could be calculated as =0.024 eV based on the Arhenius-type behavior between logo and 1/T (Fig, $5b), indicating a lower ion transport barrier. Besides, the SHE ‘was able to still stain a high ionic conductivity close to that of original condition during different healing cycle, suggesting a su- Perior self-healing property (Fis, $6). Furthermore, the linear sweep voltammetry (LSV) was used to determine the electro- chemical stability window of various electrolytes through asym- metric Znifstainless-stee! batteries. AS shown in Fi. 2i, the SHE shows a broader electrochemical stability window than that of LEing o,f Wang a areal oay Pry 202021) 008 ‘ig. 2) Composition of HE ands sealing station. b) Te ogi ost (hydrogen bon). Schematic lasaos of marpolagy elation fo 2 as with 1S (ih pre PA i) and SHES dr Zn stinging cg and PAM, especially in the positive direction, The stable voltage ‘window of SHE is ascribed that the hydrogel and more Hydrogen bond interactions can strengthen the binding force of free water ‘molecule and thus decrease reaction activity of aqueous electrolyte, 23. Zn metal depositon/stripping behavior based on the self- Ihealable hydrogel electrolyte ‘To study the influence of various electrolytes on the zinc dendrite growth, the symmetric Zn)/Zn batteries were assembled to test their long cycle stability (Fiz. 5). Comparing the surface morphology of zinc metal anodes after deposition/stripping at a ‘current density of 1.0, 3.0 and 5.0 mA em”, the SHE can prompt a “smoother and dendrite-free Zn anode after 200 cycles in contrast to thar of PAM (Vis. 32-1), and the Zn anode in LE possesses an obvious prrotuberant surface morphology after only 50 cydles (Fig. $7), Suggesting that SHE is able to homogenize the deposiionjstripping fof zine ion on the zine metal surface, As shown in the chro- hopotentiometry curves, the symmetric Z2n/SHEJZn batteries ‘exhibit a more stable and iower hysteresis of below 50 mV for 700 h than that of PAM (90 mV after 420 h) at current density of 110 mA em’? (Fig. 3 and Fig. S80), Especially, with the current density increases to 3 and 5 mA cm, the symmetric Zn(SHE/Zn batteries maintain more stable voltage hysteresis of below 100 mV for 500 h and 300 h. By contrast, the symmetric ZnjPAM|Zn bat- teries show a higher hysteresis of above 100 mV for 400 hat 3 mA cm 4, and possess ever-increasing voltage hysteresis up to 204 mV and subsequent short circuit after 266 h at 5 mA cm-? (Fig. 3h-j and Fig, S8b). Similarly, the symmetric2nj/PAM{CMC/Zn batteries stil show a short cireuit after 285 h at S mAcm”2(Fis.59), suggesting the sole CMC is not able to contribute to the dendrite- free and self-healing property of hydrogel electrolyte. Further- more, the short circuit phenomenon more likely occurred in the symmetric Zn/LE/2n batteries after 90 h, 47 h and 37 h at 10, 3.0 and 5.0 mA cm, respectively (Fis. $10a-c). In adlition, compared ‘with PAM, the symmetric Zn/SHE(Zn batteries could keep a lower and stable internal resistance during 100 cycles (Fig. 2k), which is caused by the high ionic conductivity and good interfacial ‘compatibility of SHE solid electrolyte. With the increases of cycles, the internal resistance of symmetric Zn/LE/Zn batteries was instead reduced (ig. Ila). which may be attributed to the fact that the ‘more severe dendrite growth in the LE can shorten ion distance in a ‘way until short circuit. To study the reversible Zn deposition) stripping behaviors the Znj/T batteries were assembled to perform the cyclic voltammetry (CV) a 0.5 mV s-" for various electrolytes. {As shown in Fi. 31, the SHE possesses a lower electrochemical polarization of Zn deposition/stripping than that of PAM in the ‘wide range of -0.5 to 3.0 V. Besides, the oxygen evolution potential of LE is lower than 2.5 V, and once again indicate that gel electro- Iytes (SHE and PAM) possess more stable voltage window than LE (Fig, S11), Im_a word, the highly reversible Zn anode is mainly attributed to the porous crosslinking network and more hydro- philic groups of SHE, and thus the SHE possesses high ionic con- ductivity and excellent mechanical strength. Furthermore, the hydrophilic groups on the hydrogel electrolyte interface are conductive to improve interfacial compatibility between electrode and electrolyte, which can effectively solve dendrite growth prob- Jem through lowering the overpotential of metal nucleation)ing o,f Wang a areal oay Pry 202021) 008 {40003800 BO0”2600000 TET TOOT500 10 ‘Waverunbar (cm) Z (ohm) E0335 Potential ve. 2n2n ar ig. 2 SER snag of) PAM and (4-1 SHEE een nagicaions FTIR spectro PAM and HE B) AC impedance spc the PAM and HE in the equncy ange om bil 1901 He and ane candies caelted om he peta | Linear Sweep vllanenety (SV) pt ofthe If PAM abl SHE ata ean ete of 10 Vs deposition. 24. Electrochemical performances of the flexible MnO,/SHE/Zn batteries Based on the above excellent results of SHES for high Zn?* ‘conduction and dendrite-free growth, the full battery tests were Performed on the assembled flexible zinc-based batteries. In addition, manganese dioxide (Mn0>), including a-Mn0z, B-MnO>, ‘y-Mn03,5-Mn0; and 1-Mn0>, isa widely applied cathode material in ZABs, which has both relatively high specific capacity and discharge voltage plateau compared with other electrode materials, ‘such as V-based cathodes, Prussian blue analogs (PBAs) and organic materials [46]. Thus, the Mn0>[carbon cloth has been selected as ‘cathode and matched with Zn metal anode. To prepare the flexible batteries, the MnO, cathode was blade-coated onto carbon cloth, and the flexible anode was fabricated by depositing zinc metal on the carbon cloth, And the flexible MnO,/SHE/Zn batteries were assembled to characterize the electrochemical performance (Fis). In this work, the MnO, active material is confirmed as a-phase trom XRD patterns (JCPDS: No,00-44-0141) (Fig. 12a). To further boost the electric conductivity of active material, the multiwalled carbon nanotube (CNT) was introduced into the cathode to form a three- «dimensional conductive network (Fig. $12b-d). To research the tedox activity of MnO2 in SHE, multi-sweep cyclic voltammetry (CY) is performed under different scan rates ranging from (04 mV s~" to 10 mV 5" (Fig. 4a). The shape and peak current of CV ccurves maintain a good coherence and linear relation with the increasing scan rate, suggesting a minor polarization toward the stable electrochemical reaction. And the two pairs of redox peaks appear on the CV curves under various scan rates, which belong to the extraction/insertion of H® (Peak 2 and Peak 4) and Zn" (Peak 1 and Peak 3) into a-Mn0> host, respectively [7], Besides, the CV ‘curves have been almost unchanged during 30 cycles of scanning. ‘which also prove a more reversible electrochemical cycling process {or flexible MnO;~Zn batteries based on the SHE (Fx. 4b) And the IS result of flexible MnO2~Zn batteries was displayed in Fig. 4c. indicating a smaller internal resistance ofthe full cell caused by the ‘excellent ionic conductivity and interfacial compatibility of SHE ‘membrane, AS a result, the prepared MnO,/SHE/Zn batteries delivered a reversible capacity of 304 mAh g_' close to theoretical capacity (308 mA gt) at 05 A g~',and still kept a discharge ca- pacity of 130 mah g~' at high current density of 50 g" (Fig. id nd e), which manifest an excellent rate capability surpassing most ‘of reported works [2]. And GCD of Mn02/SHEYZn batteries retain a favorable stability with returning to 0.5 A g°' after cyces of rate performance (Vig. 4). Furthermore, the Mn02/SHE/2n batteries ‘were able to preserve an approving capacity retention of 83.1% (110ing o,f Wang a areal oay Pry 202021) 008 oa ’ °. | SEE ©, 4 s 3% = 3 g Boo #00 Zoo) & s g 02) 0.2) 02) Timer ere) CRIT] moar wee} 04 ; ‘0 100 200 300 400 500 600 700 “49 700200300 400 500 : 50 100 150 200 250 300 ‘Test time (h) Test time (h) ‘Test time (h) jor Fm [ox — Heen|oe |] § = $008} c 2005 Zn dissolution 8 Liu tect " 2 vA go" = a Boor s SF Boeycle PAM 003 =< S85 oe f 2 cepoaton emma: 0.1 oS 3 00 02 04 06 08 1.0 400 800 1200 1600 O1NG EDO 05 10 15 20 25 3 ‘Area specific (mAh cm) Z (ohm) Potential (V) ig 3. SER images the 20 metal andes with) PAM and +) SHE after zn sipping for 200 cycles unde the cent ens of 1 men 2,2 mA and 5 mc ® ‘ith areal apt of Li ma em The cal a are 2m.) eng perormance of Z/SHESznsyetc cos at 1 mA cy * and 3m em, ad) the comparison of ‘Sronopatntiomeiy poles Zl smc ed ot PAR and SE at's ken? st Tie Zn platingtiping age pole at ise ees) Calvan ‘ducharge-carge curves (CED of Zn aynmetc elle tac 4) ES eats the 22 stil sed on PAN and SE before ad ar 100 es 1 caves ‘fn deposition asain in Za Fal ce athe can ate OF mV ecween 08 and 30 rah g-) at large rate of 5.0 Ag after 1500 cycles, greatly out- stripping the cycling stability of LE (33:98 capacity retention, 45,5 mAh g-') and PAM (62.5% capacity rete (ig: 4g). According to the comparison of the electrochemical per- {ormance of the MnO2i/Zn batteries based on SHEs with previous ‘works in the Table Si, the a-Mn02//2n batteries based on SHEs display a high rate-capabilty and ultrafong lifespan, surpassing. ‘that of most reported works. The highlighted rate capability and ‘ycling stability of MnO /SHE/Zn batteries is mainly derived from 809 mAh g-') stripping, and the the binding force ionic conductivity the above analytical factors: (1) The SHE can be conductive to a ‘smoother and dendrite-free Zn anode during long term deposition} ‘more hylrogen bond interactions can reinforce ‘of free water molecule and thus enhance the electrochemical stability of aqueous electrolyte. (2) The highly ‘porous 3D morphology and cross-linking networks prompt a high ‘of SHE, and the abundant hydrophilic groups of SHE skeleton can effectively improve the interfacial compatibility between solid state electrolyte and electtode materials, whiching o,f Wang a ater ody ye 202021) 008 o o cant deny A cure ensty Ag? or tao ‘ce number) ‘capaciy (mang) te nenberin) Fig. 2) Mult-sweep cic tammy (CV) of fexble2SHE|MnO, bates at ferent scan rates fom tt mi 5 CVs of exible ZSHEMN, teresa Vs ‘ting erence ES ves fei 25S; bate) CCD at vrs cen denses ranging om 5 100 ie) Rate apa of Rex ZnO; Dates at varios rts f}CCD aint even ples a0 Ag} anger ling performance ats high current density of 0A contributes to benign zine ion transport across the electrolyte and its interface to ensure an outstanding rate capability of MnOa/SHE) Zn batteries. n addition, the flexible Zn/SHE/MnO. batteries after long-term cycling still possessed a minor internal resistance vat ation compared with the original state (Fig. S13). All of these ad- vantages result ina durable cycling stability of Mn02/SHE/Zn batteries. For better revealing the stable performances of electrode material in the MnO, /SHE/2n batteries, the XRD patterns of MnO, ‘cathode and Zn metal anode at charged state were examined before and after 1500 cycles at 5.0 A/g (Fig. S14). The electrode materials both show a good structural stability without obvious irreversible phase transition. Moreover, the behavior of zinc ions insertion) ‘extraction into a-MnO» can be determined from the XPS results (Fig. 515), As shown in the XPS fitting peaks of Zn 2p, Mn 2p and © 1s, the binding energies of electronic orbits in the a-MnO2 under- ‘went a reversible variation fr zinc ions insertionjextraction during 1500 cycles, demonstrating a stable and reversible electrochemical behavior of a-MnO, cathodes in the Mn02{SHEJZn batteries for long-term cycling. 25. Self-healing property and external force resistance ofthe {flexible Mnz/SHEZn batteries ‘The self-healing property can protect the flexible batteries to stand against local stress under various deformations during their daily usage, which can greatly prolong the lifespan and reliability of the electronic system. Asan actual presentation, the flexible MnO) ‘SHE/Zn batteries could normally power a clack (ig. Sa), and the lock shut up right away when the flexible batteries was cut in half (Fig Sb) and immediately back to work after splicing the two parts (Fig Se) which confirms that the flexible MnOz/SHE|Zn batteries possess a good self-healing property Besides, the electrochemical performance of flexible MnO,/SHE/Zn batteries were measured ‘before and after multiple euting/sel-healing cyeles. ig. 5d shows EIS data of flexible batteries possess a low internal resistance and change slightly during five times of cutting/self-healing. Similarly, CV of flexible MnO3/SHE/Zn batteries exit nice repeatability for 5 cutting|slf-healing cycles, suggesting the self-healing process didn’t significantly affect the electrochemical polarization for redoxing Fa Wag a ater ody ye 202021) 008 ele Pci $ 200] bial i 1 ° o 100 200300400 0 12 14 1 0 20 4 60 80 100 120 140 160 6 zion \Btage Vm 2) ‘copy nee) g i sal gi *—*+—++_. | - e = Sd * 5 g z 7 4 § 00 Eaod nas £44 e 5 Sea : 3° ° Feed (Pristinef i Sood ‘ af aaa he 7 soar et 3 See ey ad st 2 3 4 5 ¥ 10 3030S 0 50 100 150 200 250 300 350 meno) Berean Cope rang ig 5.) Photographs of the selehealing Neb btery poweing clock before cating (efter cating ile. atersel healing (ight) ES aa and) Vo he Neale SHE 00, batteries before and after ull cing healing eyes CCD pies before and afer ipl cuisines at 30 A a) cate sponding heling icine performance Rate capably comparson a SHE, bates with psi a he rican eng ae a CCD of -SHEMND, ‘eres aer he th alc aig vaaus cent dents aging om 0 10D AE reaction (Fig. Se). Moreover, during 5 cutting/self-healing cycles, the flexible MnO /SHEYZn batteries still maintained a uniform GCD ‘curves at current density of 3.0 Alg and possessed a high healing efficiency of above 95% (Fx and g)-To show the influence of sel healing processes on the rate capability of flexible batteries, the rate performance of 2njSHE/Mn0> batteries after the firth cutting/self- healing was compared with that of the pristine one (Vis. 5h). Although the capacities of ZnjSHE/MnO> batteries at the firth ‘cutting/sel-healing state have been reduced, the flexible bateries still possessed distinct charge(discharge plateaus at 0.5 AJg. and retained no low capacities a large current densities range from 1.0, ‘lg to 10 Alg (Fig. 5i). Furthermore, the Zn/SHE/MnO2 batteries after the firth cutting/self-healing exhibited a capacity retention of, ‘80% (101 mAhjg) at 5.0 Alg after 800 cycles, indicating a decent ‘eycle performance for the self-healing flexible batteries (Fs. S16). ‘The excellent electrochemical performance of flexible batteries after the cutting/self-healing is mainly atributed to the good self- healing ability of SHE, which is displayed in Pig. $3, Besides self-healing property, the electrochemical performance of flexible ZnySHE/MnO> batteries with other extreme conditions ‘was evaluated in fig. 6, It is observed that the whole discharge ‘cues of flexible batteries via six hammerings possessed a minor fluctuation compared with inital one at current density of 3.0 Ag (Fig, 6a). Moreover, the capacity retention of flexible batter maintained 88.5% after 12 times hammer strikes (Fs. b, Fig. 173), and the each striking intensity kept approximately 20 N23 N which is calculated by equation (F (N) = 98 (Njkg) = m (kg)) from the platform scale (Fis. S17b-c), indicating an excellent mechanical property of SHE solid state electrolyte. In addition, fixed at various bending states of 30°, 60", 90° and 180°, the flexible batter retained a subtle variation of GCD curves anil high capacity reten- tion at 3.0 Ng (Fi. 6c). After 10 washing times for over 15 min pe, the flexible Zn/SHE|MnO, batteries can keep a capacity retention of ‘85.9%, and still power the electronic watch underwater illustrating highlighted waterproof mechanical capacity and adhesion force of ‘SHE Fi, 6d). To further confirm mechanical property othe flexible batteries, the 22 holes were drilled across the flexible n/SHE]Mn0> batteries and formed a typeface of HIT. And the flexible bateries still power an electronic watch without short circuit phenomenon (Fig Ge), Moreover, the electronic watch could be powered by theing Fa Wag a ater ody ye 202021) 008 a20 b120 i Brel ences, = § 216 = 60 8 3 60 $4) & $ i) 12 qo ; A ed § 20 4080 130 160-200 ° 93-46 8 1012 Specific capac (mAh g") Hammering times qi B 100] § 80 s § 60 7° 20 toe Beata foo 8 030 60 60 120 10180 ° 0 2 4 6 8 10 Specific capacity (mAh g") Wasing times e120 f 109 ite Id BG re cu 3 60 240 3 20 8 TTT TTS eT Numbers of holes ig. 6 Herochamia performance of exible 7a/SHEMAO tates in vars deste experinets)npact resistance an} casey retention of ibe ZHENG, Dates ater cilvent hammering tessa 10 Nc stato of bending exe ZySHE/MODhateries a aire! ages andthe cespondig GED cues at 30 i ‘ape ete of Peni Zi SHE/MOO, Bates fer soaking ess, punching ess.) Cut et of Nenble ZaSHEIRO, bates, flexible Mn0,SHEY2n batteries after tailoring several times, and it Prove a favorable mechanical property of SHE membrane again (Fig. 60. 3. Conelusion In summary, we successfully designed a self-healable hydrogel clectrolyte for dlendrte-free and self-healable zinc-based! aqueous batteries. The hydrogel electrolyte was synthesized by cross-linking polymerization of agarose molecular chain and PAM, and the CMC ‘was introduced into the composite electrolytes to strengthen their film-forming property. Benefiting from the highly porous 3D morphology and cross-linking networks, the SHE exhibits a high ionic conductivity of 23.1 mSjem at 25 °C, and the abundant hy- drophilic groups of SHE skeleton can effectively improve the interfacial compatibility between solid state electrolyte and elec trode material, contributing to a smoother and dendrte-free Zn anode in the symmetric batteries during long term deposition) Stripping up to 300 h at current density of 5.0 mAJem?, Assembled ‘with Znjcarbon cloth anode and a-Mn02 cathode, the flexible Zn/ ‘SHE/Mn0 batteries delivered a high capacity of 304 mAh g°' ata ‘current density of 0.5 Ag" and long cycling stability with a ca- Pacity retention of 83.1% (110 mAh” ')after 1500 charge/discharge gycles at 5.0 Ag Due to the hydrogen bonding derived from abundant hydroxyl groups in the polyelectrolyte networks, the SHE possesses a superior self-healing property and mechanical capacity ‘compared with reported works (Iable Si), which makes a-Mn0o|) 2n batteries exhibit a high healing efficiency of over 95% after 5 ‘cles of complete breakingjhealing. In addition, the Nexible Zn) ‘SHEJMnO, batteries can also power an electronic device and stand ‘against extremely harsh conditions, such as hammering, bending, drilling and tailoring, suggesting a practical value for flexible energy storage in the future. Its reasonable to believe that this work can be expected to boost the progress of high-ing Fa Wag a performance ZABs and other wearable energy storage devices. 4, Experimental section 44, Synthesis of se healable hydrogel electrolytes (SHE) ‘The SHE was prepared via a free radical polymerization under thermal curing the precursor mixture [2] First, LO g commercial agarose powder (AR grade, Alfa) was absolutely dissolved into 440 mL deionized water under extensive sttring at 95 °C for 30 min, Under cooling 080°C, the 1 mol L-' ZnSO, (AR grade, Aladdin) and (0.1 mol L~" MnS04 (AR grade, Aladdin) were added into above solution fora stirring process of 15 min, and then 30 mg potassium persulfate (AR grade, Aladdin) and 10 mg NNN-methyl- ‘enebisacrylamide (AR grade, Sigma) were sequentially added to the mixture solution. After that, 3 g acrylamide (AR grade, Aladdin) and 0.5 g carboxymethy cellulose (AR grade, Aladdin) was dissolved and stirred at 50°C for 1h, and the as-fabricated precursor solution ‘was injected into a polypropylene (PP) mold and polymerized at 70°C for 24 to obtain SHE. For comparison, polyacrylamide (PAM) ‘was fabricated as similar process as that of SHE without adding. agarose and carboxymethyl cellulose. And the liquid electrolyte (LE) was prepared through added 1 mol L' Zn$04 and 0.1 mol L* MnO, into the 20 ml. deionized water, and followed by hall-hour stirring for standby application. 42. Synthesis of Mn0@CNT cathode MnOs@CNT was fabricated via a modified co-precipitation and followed by hydrothermal method. First, the commercial carbon nanotubes (CNT) with a diameter of 10-30 nm and a length of 5-10 um (Shanghai Macklin Biochemical Co, Ltd) were refluxed in nitric acid (AR, Aladdin) at 80 °C for 6 b, and then adequately ‘washed with deionized water for several times. After that, 005g a5- Purified CNT was re-dispersed in 50 mi deionized water via mag- netic sttring for 1 h, Then, 0.98 g Mn{CH,COO),-4H1,0 (AR grade, Shanghai Macklin Biochemical Co, Ltd) was dissolved in the dispersed solution under mixing thoroughly for 30 min. Where- after, 27 ml. aqueous solution containing 0.42 g KMnOy (AR, Aladdin) was slowly added drop-wise into above solution and stirting for 30 min. After ultrasonic dispersion for 10 min, the mixed solution was transferred to a 100 mL Teflon-lined autoclave and heated at 120°C for 12 h. After cooling the obtained MnO2@CNT was collected by vacuum filtration accompanied by continuous ‘washing with deionized water, and finally dried in a vacuum oven at 80 °C for overnight. ‘To fabricate the flexible cathode, MnO,@CNT active materials, ‘Super P, and polyvinylidene fluoride (PVDF) binder was mixed in NMP (N-methyl-2 pyrrolidone) with a mass ratio of 8:1:1, and then the cathode slurry was casted on the carbon cloth and dried at a ‘vacuum oven at 80 °C for 12 h. And as-prepared flexible cathode contains approximately the active load of 1=2 mg cm 2, 43. Preparation of flexible Zn anode In order to match the flexible MnO»/SHE[Zn batteries, the Zn metal was electrodeposited on the carbon cloth substrate for Nex ible Zn anode, which used carbon cloth and zinc plate (pu rity > 99,998, Sigma) as working electrode and counter electrode in ‘an aqueous electrolyte of 1 mol L* ZnSO (AR grade, Aladdin) and ‘mol L-" KCI (AR grade, Aladdin). And electroplating process was Performed at ~0.8 V vs Zn foil for 30 min employing an electro- ‘chemical workstation (CHI 760). ater ody ye 202021) 008 44, Characterization methods ‘The morphology of gel electolytes and Zn anodes were measured via SEM (SUB020) operated at 10 kV and TEM JEM 2100) operated at 200 KY. The composition of gel electrolytes skeleton was analyzed from Fourier transform infared spectra (Wertex. 80, Bruker) with the frequency range from 400 to 4000 em The structure and phase of electrodes were determined by XRD (Djmax 2500}. And the XPS spectra of MnO;0CNT eathode with different cycles was tested by applying a Thermo Scientific ESCA Lab 250X1 instrument with 200 W Al Ks radiation an base pressure of 3» 10-" mbar in the analysis chamber 45, Electrochemical measurements ‘The ionic conductivities ofthe gel electrolytes were tested by AC impedance spectroscopy instrument from electrochemical work station (CHI 760D) with the frequency range between 0.01 and 10° Hz. The gel electrolytes were sandwiched between two stainless-steel electrodes (SS) and the Zn?” ionic conductivities (0) ‘can be calculated as following equation (1) o= dps a ‘Where d represents the distance between two SS (cm), Sis the area of the ge electrolytes (cm), and Ris the ohmic resistance (0). The activation energy Ea was calculated, according to the following Arrhenius law (2) = A-exp (-Exjgp) @ ‘where A is the frequency factor, a is the activation energy, Ris the molar gas constant and T is the absolute temperature, The elec- ‘ochemical window of electrolytes can be determined from the linear sweep voltammetry (LSV) using SSfelectrolytes[zn ata scan rate of 1 mV 5! Cyclic voltammetry (CV) curves of the flexible 'Mn0,(SHE/Zn batteries were measured based on a two-electrode system where MnO, and Zn were used as working electrode and counter electrode, respectively. The galvanostaticdischarge-charge (GCD) tests were conducted with a battery test system (Land (CT2001A) The symmetric liquid ZIBs were assembled by CR2032- type coin cells consisting of LEs, zinc electrodes and glass fber film served as separate membrane. The symmetric solid-state ZIBs ‘were assembled by the zinc electrodes and gel electrolyte in the orm of sandwich structure, And the electrochemical performance of flexible MnO /SHE/Zn batteries with planar thin film shape were performed in the voltage range of 10 V-185 V. Declaration of competing interest ‘The authors declare that they have no known competing financial interests or personal relationships that could. have appeared to influence the work reported inthis paper. Acknowledgements This research was supported by the National Natural Science Foundation of China (No. 21805063), the Natural Science Founda- tion of Guangdong Province for Distinguished Young Scholars (No. 2018803030602), the Project of Intemational Science and Tech- nology Cooperation in Guangdong Province (No. 202040505100016), the Shenzhen Sauvage Nobel Laureate Labo- ratory for Smart Materials, and Research Innovation Fund of Harbin Institute of Technology (No. HIT.NSRIF2020063).ing o,f Wang a Credit author statement YH. and W.L managed the project and guided the research; YH. and WL designed the experiment. W.L cartied out the material synthesis, characterizations and electrochemical measurements ‘with the helps from EM, Ws QL, YL, QY. and YQ, Wil involved in the discussion, W.L. wrote the manuscript with the supervision (of YH. and all authors have approved the final manuscript. Appendix A. 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