Periodic Reporting for period 4 - 3D2DPrint (3D Printing of Novel 2D Nanomaterials: Adding Advanced 2D Functionalities to Revolutionary Tailored 3D Manufacturing)
Reporting period: 2021-04-01 to 2023-03-31
Batteries store much higher energy densities; supercapacitors, on the other hand, hold one tenth of the electricity per unit of volume or weight as compared to batteries but can achieve much higher power densities.
Technology is currently striving to improve the power density of batteries and the energy density of supercapacitors.
To do so it is imperative to develop new materials, chemistries and manufacturing strategies.
3D2DPrint is developing printed micro-energy storage devices (both supercapacitors and batteries), technologies particularly relevant in the context of the emergent industry of micro-electro-mechanical systems and constantly downsized electronics.
We are using use novel two-dimensional (2D) nanomaterials obtained by liquid-phase exfoliation. This method offers a new, economic and easy way to prepare ink of a variety of 2D systems, allowing to produce wide device performance window through elegant and simple constituent control at the point of fabrication.
3D2DPrint is using our expertise and know-how to allow development of advanced AM methods to integrate dissimilar nanomaterial blends and/or “hybrids” into fully embedded 3D printed energy storage devices, with the ultimate objective to realise a range of products that contain the above described nanomaterials subcomponent devices, electrical connections and traditional micro-fabricated subcomponents (if needed) ideally using a single tool.
Objectives of the project are:
1. Development of 3D Printing Integration Models and Technologies
2. Synthesis, Purification and Liquid Phase Exfoliation of novel TMOs, LDHs, TMDs and MXenes
3. Characterisation of Liquid Phase Exfoliated 2D TMDs, LMCs, TMOs and MXenes
4. & 5. Supercapacitors and Batteries Fabrication
6. Electrochemical Characterisation of Electrodes and Performance Testing
Achievements:
- Development of 3D printed multi axis architectures
- Assembly of full supercaps and battery devices by vertically stacking of separately printed 3D architectures
- Development of 2.5 printing capabilities
Objective 2. Synthesis, Purification and Liquid Phase Exfoliation of novel TMOs, LDHs and TMDs
Achievements:
- Optimisation of the synthetic conditions for the preparation of TMOs, LDHs and MXenes (Investigation of different precursors and different wet synthetic parameters).
- Preliminary electrochemical characterisation of classically prepared electrodes
- Optimisation of the exfoliation conditions for LDHs, TMOs and MXenes (solvent selection – sonication regimes – centrifugation regimes)
Objective 3. Characterisation of Liquid Phase Exfoliated 2D TMDs, LMCs, TMOs and MXenes
Achievements:
- Full analytical characterisation of materials produced and exfoliated in objective 2 and development of high-throughput size characterisation method.
- State-of-the-art EM structural studies by aberration-corrected HRTEM and HAADF STEM
- Analytical characterisation of the exfoliated materials by atomic resolution EELS and EDX
- In-situ thermal, liquid and electrochemical characterisation of exfoliated materials on-going.
Objectives 4. & 5. Supercapacitors and Batteries Fabrication
Achievements:
- Fabrication of hierarchically structured 3D electrodes
- Manufacturing of electrodes by spraying for comparative performance evaluation
- Applying mediated drying from the liquid phase as a design tool for tuned device performance
- Assembly of hybrid electrodes based on TMDs and CNTs or graphene for batteries, LDHs, TMOs, MXenes and CNTs or graphene for supercapacitors.
Objective 6. Electrochemical Characterisation of Electrodes and Performance Testing
Achievements:
- Characterisation of the morphology of the fabricated electrodes
- Determination of the performance of the different devices fabricated under Objective 5 and 6
- Continuous feed-back to improve the performance
- Characterisation of the devices lifetime
- 2 patents as described above.
We showed that two-dimensional titanium carbide or carbonitride nanosheets, known as MXenes, can be used as the conductive-binder in thick (up to 450 μm) silicon (Si)/MXene electrodes produced by a simple and scalable slurry-casting technique without the need of any other additives. The nanosheets knit into an interconnected metallic network, enable fast charge transport and provide good mechanical reinforcement for the thick electrode. Consequently, very high areal capacity (up to 23.3 mAh/cm2) on the anode side have been realized.
Nature Communication 2019
Direct printing of functional inks is critical for applications in diverse areas including electrochemical energy storage, smart electronics and healthcare. However, the available printable ink formulations are far from ideal. Either surfactants/additives are typically involved or the ink concentration is low, which add complexity to the manufacturing and compromises the printing resolution. Here, we demonstrate two types of two-dimensional titanium carbide (Ti3C2Tx) MXene inks, aqueous and organic in the absence of any additive or binary-solvent systems, for extrusion printing and inkjet printing, respectively. We show examples of all-MXene-printed structures, such as micro-supercapacitors, conductive tracks and ohmic resistors on untreated plastic and paper substrates, with high printing resolution and spatial uniformity. The volumetric capacitance and energy density of the all-MXene-printed microsupercapacitors are orders of magnitude greater than existing inkjet/extrusion-printed active materials. The versatile direct-ink-printing technique highlights the promise of additive-free MXene inks for scalable fabrication of easy-to-integrate components of printable electronics.
Nature Communication 2019
We demonstrated rapid production of flexible MSCs is demonstrated through a scalable, low-cost stamping strategy. Combining 3D-printed stamps with arbitrary shapes and 2D titanium carbide or carbonitride inks (Ti3C2Tx and Ti3CNTx, respectively, known as MXenes), flexible all-MXene MSCs with
controlled architectures are produced. The interdigitated Ti3C2Tx MSC exhibits high areal capacitance: 61 mF cm−2 at 25 μA cm−2 and 50 mF cm−2 as the current density increases by 32 fold. The Ti3C2Tx MSCs also showcase capacitive charge storage properties, good cycling lifetime, high energy and
power densities, etc. The production of such high-performance Ti3C2Tx MSCs can be easily scaled up by designing pad or cylindrical stamps, followed by a cold rolling process. Collectively, the rapid, efficient production of flexible all-MXene MSCs with state-of-the-art performance opens new exciting opportunities for future applications in wearable and portable electronics.
Advanced Functional Materials 2018