Soft ionic conductors, such as hydrogels and ionogels, have enabled stretchable and transparent ionotronics, but they suffer from key limitations inherent to the liquid components, which may leak and evaporate. Here, novel liquid‐free ionic conductive elastomers (ICE) that are copolymer networks hosting lithium cations and associated anions via lithium bonds and hydrogen bonds are demonstrated, such that they are intrinsically immune from leakage and evaporation. The ICEs show extraordinary mechanical versatility including excellent stretchability, high strength and toughness, self‐healing, quick self‐recovery, and 3D‐printability. More intriguingly, the ICEs can defeat the conflict of strength versus toughness—a compromise well recognized in mechanics and material science—and simultaneously overcome the conflict between ionic conductivity and mechanical properties, which is common for ionogels. Several liquid‐free ionotronics based on the ICE are further developed, including resistive force sensors, multifunctional ionic skins, and triboelectric nanogenerators (TENGs), which are not subject to limitations of previous gel‐based devices, such as leakage, evaporation, and weak hydrogel–elastomer interfaces. Also, the 3D printability of the ICEs is demonstrated by printing a series of structures with fine features. The findings offer promise for a variety of ionotronics requiring environmental stability and durability.

We report a dual ionic cross-linking approach for the preparation of double-network hydrogels with robustness, high strength, and toughness, sodium alginate/poly(acrylamide- co-acrylic acid)/Fe (SA/P(AAm- co-AAc)/Fe), in a facile "one-step" dual ionic cross-linking method. We take advantage of the abundant carboxyl groups on alginate molecules and the copolymer chains and their high coordination capacity with multivalent metal ions to obtain hydrogels with high strength and toughness. The optimal SA/P(AAm- co-AAc)/Fe (SA 2 wt % and AAc 5 mol %) hydrogels showed a remarkable mechanical performance with 3.24 MPa tensile strength and 1228% strain, both of which remained stable with 76% water content and were highly swelling resistant in an aqueous environment. The hydrogels possessed high fatigue resistance, self-recovery, pH-triggered healing capability, shape memory, and reversible gel-sol transition facilitated by pH regulation. Moreover, they show three-dimensional (3D) printing processability by properly adjusting the solution viscosity. The approach may provide a convenient way of obtaining hydrogels having high strength and toughness with a number of desirable properties for a broad range of biomedical applications.

Stretchable ionic conductors such as hydrogels and ionic‐liquid‐based gels (aka ionogels) have garnered great attention as they enable the development of soft ionotronics. Notably, soft ionotronic devices inevitably operate in humid environments or under mechanical loads. However, many previously reported hydrogels and ionogels, however, are unstable in environments with varying humidity levels owing to hydrophilicity, and their liquid components (i.e., ionic liquid, water) may leak easily from polymer matrices under mechanical loads, causing deterioration of device performance. This work presents novel hydrophobic ionogels with strong ionic liquid retention capability. The ionogels are ambiently and mechanically stable, capable of not absorbing moisture in environments with high relative humidity and almost not losing liquid components during long periods of mechanical loading. Moreover, the ionogels exhibit desirable conductivity (10−4–10−5 S cm−1), large rupturing strain (>2000%), moderate fractocohesive length (0.51–1.03 mm), and wide working temperature range (−60 to 200 °C). An ionic skin is further designed by integrating the concept of sensory artificial skins and triboelectric nanogenerators, which can convert multiple stimuli into various types of signals, including resistance, capacitance, short‐circuit current, and open‐circuit voltage. This work may open new avenues for the development of soft ionotronics with stable performance.

The emerging three-dimensional (3D) printing technique has shown prominent advantages to fabricate hydrogel-based tissue scaffolds for the regeneration of bone defects.

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