Spontaneous oscillations on the order of several hertz are the drivers of many crucial processes in nature. From bacterial swimming to mammal gaits, converting static energy inputs into slowly oscillating power is key to the autonomy of organisms across scales. However, the fabrication of slow micrometre-scale oscillators remains a major roadblock towards fully-autonomous microrobots. Here, we study a low-frequency oscillator that emerges from a collective of active microparticles at the air-liquid interface of a hydrogen peroxide drop. Their interactions transduce ambient chemical energy into periodic mechanical motion and on-board electrical currents. Surprisingly, these oscillations persist at larger ensemble sizes only when a particle with modified reactivity is added to intentionally break permutation symmetry. We explain such emergent order through the discovery of a thermodynamic mechanism for asymmetry-induced order. The on-board power harvested from the stabilised oscillations enables the use of electronic components, which we demonstrate by cyclically and synchronously driving a microrobotic arm. This work highlights a new strategy for achieving low-frequency oscillations at the microscale, paving the way for future microrobotic autonomy.

The recent interest in microscopic autonomous systems, including microrobots, colloidal state machines and smart dust has created a need for microscale energy storage and harvesting. However, macroscopic materials for energy storage have noted incompatibilities with micro-fabrication techniques, creating significant challenges to realizing microscale energy systems. Herein, we photolithographically pattern a microscale Zn/Pt/SU-8 system to generate the highest energy density microbattery at the picoliter (10^-12 L) scale. The device scavenges ambient or solution dissolved oxygen for a Zn oxidation reaction, achieving an energy density ranging from 760 to 1070 Wh L-1 at scales below 100 μm lateral and 2 μm thickness in size. More than 10,000 devices per wafer can be released into solution as functional colloids with energy stored onboard. Within a volume of only 2 pL each, these microbatteries can deliver open circuit voltages of 1.16 V with total energies ranging from 5.5 ± 0.3 to 7.7 ± 1.0 μJ and a maximum power near 2.7 nW. We demonstrate that such systems can reliably power a micron-sized memristor circuit, providing access to non-volatile memory. We also cycle power to drive the reversible bending of microscale bimorph actuators at 0.05 Hz for mechanical functions of colloidal robots. Additional capabilities such as powering two distinct nanosensor types and a clock circuit are also demonstrated. The high energy density, low volume and simple configuration promise the mass fabrication and adoption of such picoliter Zn-air batteries for micron-scale, colloidal robotics with autonomous functions.

The recent interest in microscopic autonomous systems, including microrobots, colloidal state machines and smart dust has created a need for microscale energy storage and harvesting. However, macroscopic materials for energy storage have noted incompatibilities with micro-fabrication techniques, creating significant challenges to realizing microscale energy systems. Herein, we photolithographically pattern a microscale Zn/Pt/SU-8 system to generate the highest energy density microbattery at the picoliter (10^-12 L) scale. The device scavenges ambient or solution dissolved oxygen for a Zn oxidation reaction, achieving an energy density ranging from 760 to 1070 Wh L-1 at scales below 100 μm lateral and 2 μm thickness in size. More than 10,000 devices per wafer can be released into solution as functional colloids with energy stored onboard. Within a volume of only 2 pL each, these microbatteries can deliver open circuit voltages of 1.16 V with total energies ranging from 5.5 ± 0.3 to 7.7 ± 1.0 μJ and a maximum power near 2.7 nW. We demonstrate that such systems can reliably power a micron-sized memristor circuit, providing access to non-volatile memory. We also cycle power to drive the reversible bending of microscale bimorph actuators at 0.05 Hz for mechanical functions of colloidal robots. Additional capabilities such as powering two distinct nanosensor types and a clock circuit are also demonstrated. The high energy density, low volume and simple configuration promise the mass fabrication and adoption of such picoliter Zn-air batteries for micron-scale, colloidal robotics with autonomous functions.

Spontaneous low-frequency oscillations on the order of several hertz are the drivers of many crucial processes in nature [1][2][3][4]. From bacterial swimming [5, 6] to mammal gaits [7, 8], the conversion of static energy inputs into slowly oscillating electrical and mechanical power is key to the autonomy of organisms across scales [9][10][11][12]. However, the fabrication of slow artificial oscillators at micrometre scales remains a major roadblock [13][14][15][16] towards the development of fully-autonomous microrobots [17][18][19][20]. Here, we report the emergence of a lowfrequency relaxation oscillator from a simple collective of active microparticles interacting at the air-liquid interface of a hydrogen peroxide drop. Their collective oscillations form chemomechanical [21] and electrochemical [22] limit cycles that enable the transduction of ambient chemical energy into periodic mechanical motion and on-board electrical currents. Surprisingly, the collective can oscillate robustly even as more particles are introduced, but only when we add a single particle with modified reactivity to intentionally break the system's permutation symmetry [23]. We explain such emergent order through a novel thermodynamic mechanism for asymmetry-induced order [24, 25]. The energy harvested from the stabilized oscillations enables the use of on-board electronic components, which we demonstrate by cyclically and synchronously driving a microrobotic arm [26][27][28]. This work highlights a new strategy for achieving low-frequency oscillations at the microscale that are otherwise difficult to observe outside of natural systems, paving the way for future microrobotic autonomy.