3D printing of batteries literature review

Background[edit | edit source]

This page aims to review Additive manufacturing of active materials, batteries and electronics.

Search terms[edit | edit source]

3D printing of batteries

Additive manufacturing of batteries

"Direct ink printing" of "batteries"

"Direct ink printing" of "electronics"

"Fully 3d printed" battery by "direct ink writing"

Ink properties of direct ink writing

FDM printing of batteries

"FDM" printing of batteries

FDM printing of "batteries"

3D printing of batteries with "conductive polymer"

electronically conductive polymer for 3d printing

solid state electrolyte

lignin in batteries

Literature[edit | edit source]

Design and Manufacture of 3D-Printed Batteries[edit | edit source]

Lyu, Z., Lim, G. J. H., Koh, J. J., Li, Y., Ma, Y., Ding, J., Wang, J., Hu, Z., Wang, J., Chen, W., & Chen, Y, "Design and Manufacture of 3D-Printed Batteries", Joule, 5(1), 89–114, 2021

• review of techniques, materials, designs, configuration of 3D printed batteries & solutions to battery performance issues
• Conventional batteries fabrication: preparing electrode slurries, current collectors, stacking cell components, packaging, injecting liquid-electrolyte.
  • Conventional batteries challenges: can't be miniaturized & customized
• Micro-scale batteries are important for gaining high energy density & long duration
• Micro-batteries are 2D or 3D.
• 3D micro-batteries properties: higher energy & power density (because of higher active materials), higher surface to volume rations
• 3D architecture: vertically aligned nano-wires, nano-rods, nano-porous monoliths, & multi-layered stacks.
• 3D techniques: wet or dry etching, photo-patterning, sputtering, electrodeposition, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD)
• 3D printed batteries properties: high energy & power density, high shape conformability, freedom in design & shape & complex architecture, lower cost, convenient, customizable, reduce waste, less fabrication time, rapid fabrication, remove packaging step
• Types of printable batteries: solid-state Li-metal, lithium-sulfur (Li-S), lithium-oxygen (Li-O₂), Zn-air batteries
• Mechanical strength, high electronic, & ionic conductivity should be achieved in manufacturing batteries

Techniques

• 3D printing techniques for batteries: (1) material extrusion (e.g., direct ink writing [DIW], fused deposition modeling [FDM]), (2) powder bed fusion (e.g., selective laser sintering [SLS], direct metal laser sintering [DMLS]), (3) vat photopolymerization (e.g., stereolithography [SLA], digital light processing [DLP], two-photon lithography [TPL]), (4) material jetting (e.g., inkjet printing [IJP], aerosol jet printing [AJP]), (5) sheet lamination (e.g., laminated object manufacturing [LOM]), (6) binder jetting, & (7) directed energy deposition [DED] (this bullet is a copy-paste from the paper).
• This article aims to review DIW, FDM, IJP, & SLA techniques.

DIW:

• Ink: viscoelastic, rheology: yield stress behavior, elastic or storage (G') modulus, viscous or loss (G'') modulus, and viscosity (ƞ).
  • yield stress behavior: solid under low applied stress and starts to flow like a liquid above a certain level of stress
  • viscosity: ratio of the shear stress to shear rate ---> high viscosity (10⁶–10⁸ cP) and elastic behavior, shear-thinning behavior are desirable
    • low viscosity: not have enough yield stress
    • high viscosity: block the nozzle
• Advantages: most popular method for 3D printing of battery, proper for a wide range of printable materials ---> increase the possibility of using active materials for batteries, high resolution with minimum size (1 micrometer), complex architecture & design, high printing throughput, multi-material, low cost & easy to use
• Challenges: specific techniques for preparing desirable ink

FDM:

• Filament: thermoplstic, PLA, ABS, PC, PA, TPU,
• Advantages: doesn't need ink preparation, printing substrates for electrodepositing electrolyte or electrode)
• Challenges: require specific component for filament fabrication, less rage of printable materials (active materials should be embedded with thermoplastic filaments and do not come in filament form), specific filament width, lower solution (50-200 micrometer), lower throughput, lower flexible of multi-material.

Inkjet Printing:

• Two main techniques: continues & drop-on-dem & (economical & flexible in design),
• Advantages: wide range of materials, rapid prototyping, requires lower viscosity rather than DIW, multi-material (active material)
• Challenges: specific ink preparation, electrodes are in thin-film form, lower throughput, less resolution & lower size capability than DIW (10-150 micrometer)

SLA:

• Advantages: high resolution (0.5 micrometer), nozzle-free,
• Challenges: preparing printable resins including active materials+photoinitiator+prepolymers (results in low flexibility of multi-material), with proper flowability, suitable refractive index (poor refractive index---> scattering UV light--->defects, incomplete curing, bad mech prop, inaccuracy), high cost, photopolymers are sticky & messy, residual photoinitiator--->impurities & toxicity
• Two photon lithography (TPL):
  • Advantages: nonlinear two-photon absorption, high resolution (200 nanometer), fabricate electrodes, high throughput
  • Challenges: time consuming, no direct printing of the active materials by this technique

Cathode

Printable cathode materials for:

• LIBs: olivine-type lithium iron phosphate (LiFePO₄), lithium transition-metal phosphates (LiMn_1-xFexPO₄), lithium cobalt oxides (LiCoO₂), lithium manganese oxides (LiMn₂O₄), & LiNi_0.8Co_0.15Al_0.05O₂ (NCA).
  • LFP the most developed, printable by DIW, FDM, & IJP.
    • For DIW and IJP, binders and solvents for LFP are: ethyleneglycol(EG) in water, PVDF and carbon black in N-methyl-2-pyrrolidine (NMP), cellulose nanofibers in water, Pluronic F127 and black carbon in water
    • For FDM filament: PLA pellets in dichloromethane91 or 1,3-dioxolane92 + graphite = LiFePO4/PLA/carbon composites.
• Na-ion batteries: Na₃V₂(PO₄)₃ (mesh structure, DIW method), NaMnO₂ (cylinder structure, FDM method).
• Li-S batteries: Sulfur & Carbon composites
• Li-O₂ batteries: carbon-based catalyst composites
• Na-O₂ batteries: the reduced graphene oxide (rGO) with a hierarchical porous structure
• Li-CO₂ batteries: rGO framework with nickel nanoparticles
• Zn-air batteries: rGO & carbon nanotube (CNT) framework with catalyst nanoparticles
• Al-air batteries: MnO₂/CNT films
• Zn-Ag₂O batteries: Ag₂O films
• Zn-MnO₂ microbattery: MnO₂ film
• Printable phosphate cathodes (greatest proportion) >sulfur-based>carbon-based> metal oxides
• Sulfur & Carbon based cathodes are developing
• DIW>IJP>FDM

Anode

Printable anode materials for:

• LIBs: lithiumtitanate (Li₄Ti₅O₁₂) by DIW & FDM, carbon (graphite (49.2% active material+PLA+plastisizer) by FDM), & graphene), SnO₂ quantum dots, & silicon (Si).
• Na-ion batteries: graphene, TiO₂, & MoS₂-graphene composite
• Li metal are developing: theoretical capacity = 3,860 mAh/ g, low redox potential = -3.04 V----> e.g. Ti₃C₂T_x+ copper = current collector for Li metal anode
• 3D printing prevents growing Li dendrite and changing large volume interface.
• Carbon-based inks preparation: water or phenol-formaldehyde (PF) resin and SiO2 filler (requires annealing)
• DIW>FDM>IJP

Electrolyte

• 3D-printable electrolytes: polymers, polymer-ceramic hybrids, and ceramic
• hybrid type is common; controlling rheology, ion conductivity, mechanical stability, and thermal property

Printable electrolyte materials:

• poly(vinyldene fluoride) (PVDF), glycerol, and nanosized Al₂O₃ filler: rate performance, wetting characteristics, thermal stability
• Li-ion conductor Li_1.4Al_0.4Ge_1.6(PO₄)₃ (LAGP) and epoxy with SLA technique: ion conductivity and mechanical properties
• poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-co-HFP) matrices, Li+-conducting ionic liquid (Pyr₁₃TFSI and LiTFSI salt), and TiO₂ nanoparticle filler with DIW technique
• LiTFSI, polyethylene oxide (PEO), and PLA with SiO₂ or Al₂O₃ filler with FDM technique: mechanical properties and high-temperature durability
• poly(ethylene glycol) (PEG) with SLA technique
• PEO polymer with LiTFSI salt with FDM technique: high ion conductivity
• ceramic Li₇La₃Zr₂O₁₂
• photopatternable electrolyte through a Li+-conducting ionogel with SLA technique

Current collector

• gold (Au) with lithographic patterning and e-beam deposition
• metallic: Ni, Cu, Ag/Zn---> e.g. synthesizing a Ni paste comprising Ni flakes, Ni nanoparticles, and a photoreactive polymeric binder, polyvinylpyrrolidone (PVP) in terpineol, DIW and flash-light sintering

Separator

• integrating boron nitride (BN) nanosheets into PVDF-co-HFP with extrusion: uniform thermal distribution interface, homogeneous Li nucleation, prevent Li dendrite growth, proper electrochemical performance
• composite of LiTFSI/propylene carbonate (PC) electrolyte, photocured acrylate resin, a photoinitiator, and Al₂O₃ particles fillers

Packaging

• epoxy and fumed SiO₂
• ABS case with FDM technique for replaceable electrodes and electrolytes
• SLA technique for aqueous zinc-ion batteries

Construction of Electrodes

• could be direct or post-treatment needed (solvent evaporation, freeze-drying, annealing, physicochemical treatments, and photo-/thermo-curing) ---> for achieving high electrically conductive properties, electrochemical activity, and mechanical stability| may lead to shrinkage and distortion---> decrease repeatability
• Types: direct printing, conversion, deposition, and filling
  • Direct: no post-treatment, solvent removed by vacuum or freeze drying
    • DIW: carbon-based electrodes, e.g. graphene oxide (GO) and the ultralight GO aerogel
    • FDM: degrading PLA + yielding garphene anodes and LFP cathodes
  • Conversion: requires post-treatment, most common for electrodes
    • LiFePO₄, LiCoO₂, LiMn_1-xFe_xPO₄, and Li₄Ti₅O₁₂, carbon-based electrodes (metal-organic-framework (MOF)-derived carbon framework, active carbon/CNT/rGO composite)
  • Deposition: deposition active materials on 3D-printed substrates.
    • LiFePO₄ and Li₄Ti₅O₁₂ on perforatedpolymer substrates, palladiumonSLA-basedpolymers, polypyrroles electrodeposited on the graphene-based conductive filament, and high mass loading of MnO₂ on a porous carbon aerogel scaffold.
  • Filling: filling active materials into the 3D-printed porous substrates or templates
    • electrode materials ink filled into 3D porous gel polymer electrolyte
    • ceramic Li+ conductor LAGP filled into the polymer template as the electrolyte

Architecture of Electrodes

• Types: thin films, porous frameworks, surface patterns, and fibers
  • Thin films: common and available, by IJP, assembled into 2D stacked batteries
  • Porous frameworks: by DIW, FDM, and SLA, micro-, meso-, to macrosize pore, proper for configuration sandwich-type, in-plane type, and concentric tube type.
  • Surface patterns: less common for electrodes, proper for solid-state electrolyte
  • Fibers: common;
    • e.g. LFP & LTO fibres by DIW, (+CNT+ active materials+ PVDF+ NMP)

Battery Configuration

• Types: sandwich-type, in-plane type, concentric tube type, and fiber-type
  • Sandwich-type: classic, economical, rapid, stacking, round, square, triangle, and pentagon, large
  • In-plane type: classic, microscale, electrodes are parallel, in same plane, easy ion transfer
  • concentric tube type: unique, vertical electrodes cover by solid-state electrolyte, filled by counter electrode material, common in micro, silicon anodes, (SLA method, polymer substrate+ thin-film electrode+poly-ceramic electrolyte with electrophoretic deposition)
  • Fiber-type: unique, two wire-shaped electrodes are twisted together, flexible and wearable
    • e.g. all-fiber quasi-solid-state LIBs, coated by polymer gel electrolyte, DIW technique
• Challenges: mechanical properties; solutions: 1- adding fillers in inks or filaments (silica, cellulose, carbon), 2- manufacturing polymer scaffold coated by active materials
  • BUT result in reducing active materials ratio and energy density!

Performance

• thickness: 0.05 mm to 1 mm, areal energy: 1 mWh/ cm² to 20 mWh/ cm²
• 3D printed LFP higher capacity than coating method
• 3D-printed LIBs: areal energy >30 mWh/cm², power densities >1,000 mW/cm²
• 3D-printed Zn-Ag₂O millimeter battery: current densities (1–12 mA/cm²), areal capacity of 11 mAh/cm
• 3D-printed Zn/MnO₂ microbattery: volumetric energy density of 17.3 mWh/cm (more than Li thin-film batteries: <₌10 mWh/ cm3)
• 3D-printed dual-ion microbattery: ultrahigh volumetric energy density of 291 mWh/cm3 at 1 C and an ultrahigh volumetric power density of 1,756 mW/cm3 at 5 C.

Design challenges

• Solid-state batteries challenges: low ionic conductivity (in polymers), poor mechanical properties (in ceramics), high cell resistance
• solution for ionic conductivity and mechanical properties ---> hybrid: e.g. 3D printed polymer template filled with ceramic Li+ ion conductor LAGP (pathway)--> sinter--->remove polymer---> filled with non-conducting polypropylene or epoxy polymer (mechanical properties)
  • gyroid microarchitecture template---> proper mechanical prop & high ionic conductivity = 1.6 * 10�^-4 S/cm
• solution for high cell resistance: e.g. extrusion of ceramic Li7La3Zr2O12 solid electrolyte (surface pattern)---> decreasing resistance & increasing energy and power density.
• Li metal anode challenges: oxidation and safety issues
• solution: 1) using solid electrolyte inter-phase mimic (pSEI) on the Li surfaces, organic part: moisture-repellent, inorganic: Li⁺ transport.
• 2) extrusion of zinc-based MOF precursor ---> N-doped carbon: prevents Li dendrite, proper Li deposition, stabilized Li/electrolyte interface, and dissipated high current densities---> high areal capacity 30 mAh/cm² (at high rate of 10 mA/cm²)
• 3) carbon-Cobalt framework by extrusion: good conductivity & mechanical properties, micropores act as accommodation for Li₂O₂ ---> avoid surface passivation, increasing specific energy: 798 Wh/kg
• Microfluidic network in redox flow cells: e.g. 3D printed polymer+ sputtering Ni/ C)---> electrolyte place in multiple-passes: maximum power density of up to 1.4 W/cm2 & net power density of up to 0.99 W/cm2
• Safer LIBs: CNT-wrapped thermoresponsive polyethylene microspheres on electrodes (FDM method) ---> 1) PE film prevent ionic flow @ high temperatures---> shutdown, 2) exact deposition of CNT-coated PE microspheres onto electrodes ----> shutdown

Future work

• increasing mechanical properties of electrodes as well as electrochemical performance by: post-treatments (thermal sintering) & evaluating starting materials (reinforcing additives)
• other techniques: continuous SLA, aerosol jet printing (AJP), electrohydrodynamic (EHD), nanoimprinting
• 4D printing

Additive Manufacturing of Batteries[edit | edit source]

Pang, Y., Cao, Y., Chu, Y., Liu, M., Snyder, K., MacKenzie, D., & Cao, C. "Additive Manufacturing of Batteries", Advanced Functional Materials, 30(1), 1906244, 2020

• 3D printed-battery advantages: complex architecture, shape & thickness, SSE, economical, clean, easy to operate, fewer fabrication steps

Techniques

• Lithography-based Printing (HL), Template Assisted Electrodeposition (TAE), Inkjet Printing (IJP), Direct Ink Writing (DIW), Fused Deposition Modeling (FDM), Aerosol Jet Printing (AJP) (Table 1 in the paper)

Lithography-based Printing:

• 1) Holographic lithography (HL)+ photolithography ---> LIB (simple & low cost)
• 2)Projection microstereolithography (PµSL) ---> 3D microbattery (poor cycle performance and low capacity)
• 3) SLA high spatial resolution, e.g. perforated spherical, cylindrical and cubic polymer substrates with high surface area (done)

Template-assisted electrodeposition (TAE):

• Most common, tunable pore size, economical, versatile, easy to control, nanostructured electrodes with supercapacitor-like charge/discharge rate while retaining comparable battery-like storage capacity
• Challenges: not rapid, high pores ---> poor mechanical properties

Inkjet printing (IJP):

• Complex shapes, high resolution, tunable thickness, electrodes with high specific surface area, multi-material
• Challenges: low printing speed and high requirements for preparing inks, head prone to clog and damage
• e.g. thin film silicon anode for LIBs
• e.g. LiMn _0.21 Fe_0.79 PO₄ @C (LMFP) nanocrystal cathodes

Direct ink writing (DIW):

• gel-based viscoelastic ink, shear thinning
• low-cost, easy to operate, material diversity, maskless process, capable of printing all components
• Challenges: requiring gel-based viscoelastic, high yield stress and storage modulus inks, poor mechanical properties
• e.g. LIBs with thick electrodes
• e.g. 3D electrodes with SnO₂ quantum dot inks
• e.g. MOF-derived hierarchically porous framework for Li-O₂ battery

Fused deposition modeling (FDM):

• widely used, complex objects, no waste, user friendy, economical, high rate, large size, no chemical post-processing
• e.g. graphene composite structures
• e.g. anode of graphite/polylactic acid (PLA) filament

Aerosol jet printing (AJP):

• wide range materials (dielectrics, conductors, semi-conductors and encapsulation materials), non-contact, no mask, high resolution, 2D electronics circuits and electronics

Electrode

• Carbon-based, Cellulose nanofiber-based, Li4Ti5O12/LiFePO4 based

Carbon-based:

• Graphene oxide: ink-formation ability, viscoelastic, thermal annealing---> Reduced graphene oxide (rGO)
  • rGO: good electrical conductivity, common (aerogel microlattices, nanowires, periodic scaffolds, complex networks
• CNT: Multi-Walled Carbon Nanotubes (MWCNT) electrodes
  • MWCNT: high conductivity, ultrahigh porosity

Cellulose nanofiber-based (CNF):

• high solubility in water, high viscosity inks, conductive additive, charge collector, and porous scaffold
• carbonized CNFs + LFP + oxidation treatment ---> interdigitated cathode
• carbonized CNFs + Li metal+ oxidation treatment ---> interdigitated anode

Li4Ti5O12/LiFePO4 based (LTO & LFP):

• most common, low volumetric expansion, high rate capability, high stability, safe.
• Challenges: lower long-term cyclability of packaged battery

Electrolyte

• high ionic conductivity, low electronic conductivity, and low activation energy electrolytes are being investigated
• inorganic electrolytes: poor chemical/electrochemical stability and low mechanical flexibility ---> all-solid-state Li-ion battery with gel composite electrolytes (GCE) ---> increasing safety
• e.g. flexible ceramic-polymer electrolytes (CPEs)
• e.g. hybrid solid-state electrolytes without any post-treatment procedure (PVDF-HFP matrices for mechanical support + Li-ionic liquid)
• e.g. garnet-type Li7La3Zr2O12 (LLZO): nonflammable and high electrochemical stability with Li metal

Future work

• new electrochemically active materials
• larger specific surface area
• not post-treatment needed & advanced 3D printing techniques
• Packaging and encapsulation

Recent Development of Printed Micro-Supercapacitors: Printable Materials, Printing Technologies, and Perspectives[edit | edit source]

Li, H., & Liang, J. "Recent Development of Printed Micro-Supercapacitors: Printable Materials, Printing Technologies, and Perspectives". Advanced Materials, 32(3), 1805864, 2020

• supercapacitors: ion adsorption–desorption & Faradaic reaction between the electrode and electrolyte (separator sandwiched between two electrodes)
• micro-supercapacitors (MSCs): interdigitated finger electrodes
  • Advantage: increasing energy density without loss of power denssity & low cost
  • Challenge: assemble
• 3D printing of MSC advantages: independent of substrate---> various materials & environmentally friendly
• 3D printing of MSC challenges: ink rheology, compatibility of in with substrate

Ink:

• Newtonian & non-Newtonian
  • non-Newtonian: time-dependent or time-independent
    • time-independent: shear thickening behavior (not popular), shear thinning (pseudoplastic), Bingham behavior (hybrid of Newtonian & non-Newtonian)
    • time-dependent:
      • Rheopexy (time-dependent dilatant behavior): viscosity increase by time
      • Thixotropy (timedependent pseudoplastic behavior): viscosity decrease by time (gels)

Resolution:

• 1-500 micrometer
• depend on printing process, ink properties, substrate & post-processing

Electrode

• active nanoparticles (electrochemical property), inactive organic binder/additives (printability, require aggressive post-treatment to be removed), solvents (wettability, dispersion stability, and uniformity of the active particles)

Graphene-Based:

• theoretical surface area (2630 m2 g−1), exceptional electronic properties, mechanical strength, and flexibility
• store energy through fast ion adsorption-dislodging
• act as electrode and current collector
• Challenges: compatibility, Repeatability and controllability, post-treatment
• Exfoliation method for graphene ink:
  • e.g. graphite flakes in N,N-dimethylformamide (DMF) through sonication+ solvent exchange of DMF with terpineol+ ethyl cellulose---> inkjet perinting---> 300 micrometer (post-treatment required)
  • e.g. electrochemically exfoliated graphene (EEG) (high yield (>85%, ≤3 layers), large lateral size (up to 44 µm), low oxidation degree (a C/O ratio of 17.2), hole mobility of 310 cm² V⁻¹ S⁻¹, high graphene concentration up to of 2.3 mg mL−1, lifetime, jet performance,---> inkjet perinting
  • developing methods to reduce post-processing time:
    • e.g. pristine graphene 2 nanometer thickness & 200 nanometer latera: EEG by graphite flake+ ethyl cellulose---> graphene/ethyl+ 14:3:3 cyclohexanone/ terpineol/di(ethylene glycol) methyl ether---> graphene ink ≈15 mg mL⁻¹ of graphene & 8–12 mPa s viscosity
    • e.g. hybrid ink: EEG+ poly(3,4-ethylenedi oxythiophene):poly(styrenesulfonate) (PEDOT:PSS)
• Dispersed GO-based ink:
• GO---> active material & additives as stabilizer or binders
  • e.g. GO + polyaniline (PANI)---> smart applications
  • e.g. GO + commercial pen ink---> reduce agglomeration
• low GO concentrations ---> proper for inkjet printing and spray-coating
• high GO concentration---> proper for gravure printing, screen-printing, and 3D printing
  • residual oxygen---> increase the total capacitance
  • e.g. GO ink---> gravure printing---> highly porous electrodes on polyimid---> high areal specific capacitance (6.65 mF cm⁻²), high energy density (1.41 mWh cm⁻³ at 25 mW cm⁻³), and high power density (0.35 mWh cm⁻³ at 300 mW cm⁻³)

MXene-Based:

• MAX (A= AL or Ga)---> MXT (M= Mo, Ti, Nb, X= N, C, T= OH, =O, -F)
• higher conductivity than graphene
• storage capacity & release energy @high rates
• active material & current collector
• no need to surfactant or polymer additives
• environmentally friendly, scalable, facile, no harsh post-processing
  • e.g. Ti₃C₂T_x: volumetric capacitances ≈900 clay electrode and 1500 F cm⁻³ hydrogel electrode
  • e.g Ti₃C₂T_x, lateral dimension of 1.2 ± 0.2 µm and thickness of ≈1.5 nm, PET substrate---> areal capacitance of 61 mF cm⁻² at 25 µA cm⁻² ---> durable, high energy and power density
    • challenges of symmetrical Ti₃C₂T_x: poor uniformity, low resolution (gap more than 550 micrometer), low areal capacitance, low rate performance, limited operating voltage (0.6 V)---> oxidation, energy density= 3.38 µWh cm⁻²
    • solution: asymmetrical Ti₃C₂T_x=anode, Co-Al layered double hydroxide=cathode---> operating voltage= 1.45 V, energy density= 8.84 µWh cm⁻²

Pseudocapacitive Material-Based:

• transition metal oxides or nitrides, conductive polymers
• reversible electrochemical redox reactions
• larger specific weight
• higher volumetric capacitance
  • challenges: low to moderate electrical conductivity, limited cycling stability, and poor solubility, limited energy storage capacity at high rates, limit the capacitance
  • solution: amalgamate additional components: non-Faradaic electrode materials, highly conductive particles, other additives to form a nanocomposite-based ink
    • e.g. MnO₂/OLC (20–30 nm)+carbon black + poly(vinylidene fluoride) (PVDF)---> screen-printed, 300 µm finger gaps on PET and paper substrates ---> capacity = 7.04 mF cm⁻² at a current density of 20 µA cm⁻²
    • e.g. silver nanoparticles into PPy+ carbon black---> energy density=0.00433 mWh cm⁻²
    • e.g. PEDOT:PSS+ polyurethane, polyethylene oxide, Triton x-100, and Tween 80---> electrical conductivity & capacity, specific capacitance= 6.4 mF cm⁻²

Current collector

• full contact with the electrode
• low resulting junction resistance
• conventional: Au, Cu, Pt, Ni foil
  • e.g. current collector: silver paste+PET+heat, electrode: N-doped rGO and PVDF (4:1 in weight), surface area (431 m² g⁻¹)---> specific areal capacitance of 3.4 mF cm⁻²
• challenges: brittleness, weak interface
• solution for brittleness: metallic nanowires
  • e.g. silver nanowires (AgNWs): diameter= 20-100 nm, length: 20-100 micrometer coated with poly(vinylpyrrolidone)---> high electrical conductivity, high mechanical properties
  • e.g. silver nanowires + (hydroxypropyl)methyl cellulose, fluorosurfactant, and an antifoaming agent as organic additives---> resolution: 50 micrometer, electrical conductivity of 4.67 × 104 S cm⁻¹ & stretchability
• solution for weak interface: highly active materials for both electrode and current collector:
  • AgNWs as the current collector & conducting bridge
  • improve single-walled carbon nanotube (SWCNT) electrodes
    • AgNWs into the SWCNT/AC network

Electrolyte

• liquid electrolytes (aqueous or organic-based solutions) & solid-state electrolytes (gel-type)
• Factors: electrical insulation, ionic conductivity, voltage window, electrochemical stability, ionic radius
• liquid electrolyte---> encapsulation needed: in low temp, leak-proof, compatibility ---> solid-state MSCs
  • solid-state electrolyte: dissolve acids, alkalis, salts, or ionic liquids into a polymer, such as poly(vinyl alcohol) (PVA), polyacrylonitrile, PVDF, poly(4-styrenesulfonic acid) (PSSH), poly(styrene-b-methylmethacrylateb-styrene) (PS-PMMA-PS), or UV-curable precursors such as ethoxylated trimethylolpropane triacrylate
  • easy to process, high mechanical properties
  • e.g. PSSH with phosphoric acid and ethylene glycol+graphene electrodes

Techniques

• Inkjet printing, screen printing, 3D printing

Inkjet Printing:

• Low throughput, high resolution
• e.g. AC/CNT-based finger electrodes, AgNW based interdigitated current collectors, and ionic liquid/ultraviolet-cured triacrylate polymer-based solid-state electrolyte ---> dimensional integrity, mechanical flexibility, and good electrochemical performance
• e.g. PEDOT:PSS-CNT/silver nanoparticle as the electrode material ---> rate capability up to 10 000 mV s⁻¹, volumetric specific capacitance (23.6 F cm⁻³)
• Multiple MSCs---> require repeatability, simplicity and reliability---> inkjet printing
• e.g. lamellar potassium cobalt phosphate hydrate (K₂Co₃(P₂O₇)₂·2H₂O) nanocrystal whiskers (positive electrode), graphene nanosheets (negative electrode), PET (substrate)---> potential window of 1.07 V, specific capacitance 6 F cm⁻³, current density of 10 mA cm⁻³

Screen Printing:

• continuous, 30-50 micrometer resolution, thick patterns more than 10 micrometers
• pressing the ink---> prepatterned masks
• no need to vaccum---> rigid and flexible substrates are desirable
• depend on: ink stenciling and print-ability, affinity between ink and substrate
• Challenges: requires high viscosity ink, shear-thinning, inactive additives
• e.g. MnO₂/OLC (active material), PVA/H₃PO₄ (solid electrolyte), 10 micrometer, specific areal capacitance of 7.04 mF cm⁻²
• e.g. FeOOH/ MnO₂ + acetylene black + LA133 solute---> area specific capacitance of 5.7 mF cm⁻², energy density of 0.0005 mWh cm⁻² at a power density of 0.04 mW cm⁻², mechanical properties
• e.g. Ag@PPy@MnO₂ cathode + AC anode + PVA/Na₂SO₄ gel electrolyte+ Ag current collector---> potential window 1.6 V, areal capacitance of 95.3 mF cm⁻² at 5 mV s⁻¹, energy density of 0.0337 mWh cm⁻², power density of 0.38 Mw cm⁻²

3D Printing:

• CAD design
• desirable for lithium–sulfur batteries, lithium-ion microbatteries, and MSCs
• e.g. CNT + ethylene glycol+ isopropyl alcohol---> extrusion---> solid-state MSC---> areal capacitance of 4.69 mF cm⁻² at 50 mV s⁻¹
• e.g. GO gel+ gold current collectors--->extrusion---> freezedrying, reducing, and vacuum drying---> high area capacitance of 56.7 mF cm⁻² at a scan rate of 5 mV s⁻¹
• e.g. PANI/GO gel inks (1mm thick)--->areal specific capacitance of 1329 mF cm⁻²
• e.g. GO/PA-PE (positive electrode), rGO-PEDOT:PSS (negative electrode)---> extrusion---> areal capacitance of 153.6 mF cm⁻² at 5 mV s−1, potential window of 1.2 V, energy density (from 3.36 to 4.83 mWh cm⁻³), power density (from 9.82 to 25.3 W cm⁻³)

Gravure Printing:

• high speed and high resolution
• e.g. N-doped graphene and PVA-H3PO4 gel electrolyte---> areal capacitance of 37.5 mF cm⁻² at a scan rate of 5 mV s⁻¹, energy density of 5.20 µWh cm⁻²

Spray Printing:

• e.g. MnO2 nanosheets/PH1000 (MP) (positive electrode)+ EG (negative electrode) + LiCl/PVA gel electrolyte--->spray printing--->volumetric energy density of 6.6 mWh cm⁻³, planar, flexible, high-voltage, micro energy storage devices

3D-printed electrodes for lithium metal batteries with high areal capacity and high-rate capability[edit | edit source]

Lyu, Z., Lim, G. J. H., Guo, R., Pan, Z., Zhang, X., Zhang, H., He, Z., Adams, S., Chen, W., Ding, J., & Wang, J. "3D-printed electrodes for lithium metal batteries with high areal capacity and high-rate capability. Energy Storage Materials, 24, 336–342, 2020

• Lithium metal---> not safe
• solution: modift electrolyte, interface between Li and electrolyte, modify anode structure
• this work: LFP cathode, N-doped carbon framework from Zn-MOF (avoid dendrite, place for Li, stabilize Li/ electrolyte interface)---> extrusion---> Li deposition---> areal capacity 30 mAh cm⁻² at current density 10 mA cm⁻² rate, operate at current density 20 mA cm⁻²

Energy storage: The future enabled by nanomaterials[edit | edit source]

Pomerantseva, E., Bonaccorso, F., Feng, X., Cui, Y., & Gogotsi, Y. "Energy storage: The future enabled by nanomaterials". Science, 366(6468), eaan8285, 2019

• Quality of printed battery: stability of activr nanomaterial-based ink, dipersibility in solvent, thickness
• 0D & 2D sheets: better for printing than CNT
• Battery location in the device---> mey be subjected to hit...---> stable electrolyte, ceramic separators, such as ceramic nanofibers, boron nitride, or clay
• miniaturized electronics---> use nanomaterials in active and nonactive components.

Recent progress on printable power supply devices and systems with nanomaterials[edit | edit source]

Lin, Y., Gao, Y., Fang, F., & Fan, Z. "Recent progress on printable power supply devices and systems with nanomaterials". Nano Research, 11(6), 3065–3087, 2018

• Printing---> tansistors, photodetectors,sensors,

Techniques

Screen printing:

• resolution 6 micrometer, high viscosity and shear thinning behavior ink, certain wastage, mask defined design, printing speed 70 m·min^–1, mass production, practical for electronic devices, wide range of materials
• challenge(s): low design flexibility

Inkjet printing:

• 2 micrometer resolution, ink viscosity (low), ink composition, ink concentration, drop-on-demand, maskless, 1 m·min^–1
• challenge(s): aspect ratios of active materials---> restricted by nozzle size

3D printing (extrusion):

• complicated geometeries, nano to macro
• 10 micrometer resolution, shear thinning behavior and quick solidification ink, drop-on-supply, maskless, 4 m·min^–1
• ink rheology: electrically insulating additives (viscosifiers, ultraviolet light (UV) curable gels)
• challenge(s): materials and methodes for furthur resolusion and performance

Laser-based:

• 500 nanometer resolution, Thermally convertible ink, In situ patterning, Maskless, 10 cm·min^–1
• graphene oxide (GO)---> laser--->rGO
• molybdenum disulfide (MoS₂), molybdenum trioxide (MoO₃), tungsten disulfide (WS₂), boron nitride (BN) nanosheets
• challenge(s): Materials for laser-based are not explored for energy devices, need low speed---> low efficiency

Gravure printing:

• mass production
• challenge(s): hard to get uniform pattern, resolusion and design limited to cylander patterns (made by laser cutting or electromechanical)---> maintanance cost

Transfer printing:

• e.g. microscale solar cells---> 43.9% power conversion efficiency

Aerosol jet printing (AJP):

• mask-free, non-contact, drop-on-demands, line width 10 micrometers (thin film deposition), metal contact preparation in the solar cell, perovskite films (fewer labour required)
• challenges: ink preparation, low-temperature post-treatment, produce fine-egded patterns

Printable energy conversion devices

solar cells:

• photon energe>band gap---> electron-hole-->seperated by existing electric field--->external circuit
• Si-based, OSCs, DSSCs, PVSCs
• Printing: large scale, flexible, smooth surface required
• Structures and materials---> important to investigate for 3D printing.
• Nanocrystal ink: e.g. synthesized copper indium gallium selenide (CIGS) nanocrystal (not fully printed)
• e.g. tandem OSCs with printed Ag and Ag nanowire network as the electrode (fully printed)
• e.g. DSSC by inkjet printing an ionic liquid electrolyte
• perovskite solar cells: hard to print, sensitive to humidity, decomposition (consist of hole transporting layer (HTL), electron transporting layer, perovskite layer and two electrodes)
• e.g. no HTL---> fully printed
  • modify: perovskite layer devide: mesoporous TiO2, ZrO2 and porous carbon film by screen printing
• modifying interface morphology:
• modifying crystallinity: antisolvent then active material printing (dual-nozzle inkjet printing)---> single crystal

Other energy conversion devices:

• mechanical stress/strain---> in piezoelectric materials
• e.g. lead zirconate titanate (PZT) and barium titanate (BTO) by 3D printing---> ceramic piezoelectric materials
• e.g. Poly(vinylidene fluoride) (PVDF) --->screen print between printed Ag electrode
• pizoelectric+ ZnO nanowires----> piezoelectric nanogenerators (PENGs)
• triboelectric nanogenerators (TENGs)---> electricity by friction (attractive for 3D printing)---> most parts are 3D print of PLA (low cost, non-toxic)
• Bioenergy: biofuel cells (BFCs)
• glocose & lactate ---> oxidized---> electricity

Printable fabrication of energy storage devices

• supercapacitors and rechargeable batteries
• roughness and porousity are important

Supercapacitors:

• large electrode surface area, multiple charge storage mechanisms, deliver energy faster (than rechargable batteries)
• in electric vehicles and medical treatment
• Carbon-based ink: electrode
  • store energy though physical ion absorption---> electrical double layer capacitor (EDLC)
  • low resistance, high porosity, mechanical stability, electrochemical stability
  • For increasing capacity: use transition metal oxides (manganese dioxide (MnO2), ruthenium dioxide (RuO2), etc.), transition metal nitrides (titanium nitride (TiN), ruthenium nitride (RuN), etc.), and conducting polymers (polypyrrole (PPy), polyaniline (PANI), etc.)
  • For preventing agglomeration and decreasing surface tension: Surfactant (dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS)):
  • For tunning the viscosity, surface tension, ink concentration: conductive polymeric binders
  • substrates: PET, printing paper, textile
• laser reduction of GO films or laser carbonization of polymer sheets
  • GO+water---> seperator & electrolyte
• Callenge: low normalized areal capacitance: 20 mF·cm^–2
• solution: 1) nanostructures & 2) increasing the electrode density ---> energy storage capacity, fast charging, long cycle life and high compatibility
  • 1) e.g. millimeter ultrathick electrodes with periodic macropores by 3D printing of graphene aerogel--->high aspect ratio structures & control porosity, mechanical properties
  • 1) e.g. combine printing & conventional: laser-scribing printing--->highly porous rGO & electrochemical deposition---> deposit MnO2 ----> areal capacitance of up to 400 mF·cm–2
  • 2) e.g. inkjet printing and electrochemical depositions---> interspace of 5 μm--->specific energy & power

Rechargeable batteries:

• higher energy density, more stable, lower self- discharging rate
• ion intercalation/deintercalation into the bulk electrode
  • e.g. polystyreneblock-polyisoprene-block-polystyrene (SIS) as hyperelastic binder in zinc-silver oxide (Zn-Ag2 O) ---> reversible capacity density (2.5 mAh·cm^–2) at discharge current of 3 mA·cm^–2
  • e.g. single-wall carbon nanotubes & conductive straight-chain sulfur---> lithiumsulfur cathodes---> inkjet printing--->capacity of around 800 mAh·g^–1
  • e.g porous polymer electrolyte by adding Al₂O₃ ---> wetting characteristics & high thermal stability

Printable fabrication of Self-powered energy source

Prototype:

• photovoltaics-battery, photovoltaicssupercapacitor, nanogenerator-supercapacitor
• e.g. LIB photo-charging by a perovskite solar cell
• e.g. hybrid energy conversion devices: solar cells and a nanogenerator, energy storage: supercapacitor----> ZnO nanowires and graphene on a single poly(methyl methacrylate) (PMMA) fiber coated with Au)common electrodes)

Research advances:

• e.g. printable PVSC + electrochromic battery (WO3 nanowires as anode materials and NiO/rGO as cathodes)
• e.g. crystalline Si photovoltaics (SiPV) + LIB (all-solid)---> screen printing, well-packaged

Direct Ink Writing of Materials for Electronics-Related Applications: A Mini Review[edit | edit source]

Hou, Z., Lu, H., Li, Y., Yang, L., & Gao, Y. "Direct Ink Writing of Materials for Electronics-Related Applications: A Mini Review". Frontiers in Materials, 8, 2021

• DIW: complicated structures, higher accuracy, improved efficiency, enhanced performances
• DIW depends on: direct writing parameters (pressure, speed, and nozzle size) and printing environments (temperature, direct writing medium)
• DIW material range: metals, ceramics, polymers, and composites
• DIW material properties: high shear-thinning behavior & viscoelasticity, high solid content (avoid changes of volume and shape)
• DIW ink include: sol-gels, polymer melts, wax-based materials and polyelectrolyte, nano-materials as fillers
• graphene oxide (GO) filler: rheology
• silane-treated hexagonal boron nitride nanosheets fillers: electrical conductivity
• TiO2 nanoparticles fillers: thermal conductivity
• Al2O3 nanoparticles fillers: ionic conductivity
• Pt nanoparticles fillers: electro-activity
• Electrode:
  • e.g. LFP (LiFePO4)/GO and LTO (Li4Ti5O12)/GO polyvinylidene fluoride (PVDF, as binder) and carbon nanotubes (CNTs, as conductor)
  • e.g. CNTs/V2O5 fiber cathode and CNTs/VN (vanadium nitride) fiber anode
• Electronic Circuits:
  • reduced graphene oxide (rGO) and poly(lactic acid) (PLA)
  • polyvinyl alcohol to modify the commercial carbon paste ink
  • gallium and its alloys
  • low cost paper as substrate: e.g. direct writing of liquid metal on paper, mixed liquid Ga75.4In24.5 alloy and nickel powder to form a sticky ink---> plasticity, adhesivity
  • e.g. polypyrrole into graphene/carbon black composite, using a mixture of alcohol, ethylene glycol, glycerol and deionized water as solvent + high-gloss photographic paper substrate
  • e.g. additive-free Ti3C2 MXene-inwater inks+ paper, textile, wood and plastics substrate
• Functional Components:
  • sensors, transistors, light emitting diodes, antennas
  • aqueous ink based on polydimethylsiloxane (PDMS) submicrobeads/GO nanocomposite
  • e.g. acrylamide, an ultraviolet initiator, and the poly(butyl acrylate) spheres (160 nm) swollen by 2-ethylhexyl acrylate monomers, to construct a mechanochromic sensor
  • e.g. Fe and Cu particles onto the glass substrate for sensing acetone gas
  • fully 3D printed organic electrochemical transistors (OECTs)

Direct Ink Printing of PVdF Composite Polymer Electrolytes with Aligned BN Nanosheets for Lithium-Metal Batteries[edit | edit source]

Rasul, M. G., Cheng, M., Jiang, Y., Pan, Y., & Shahbazian-Yassar, R. Direct Ink Printing of PVdF Composite Polymer Electrolytes with Aligned BN Nanosheets for Lithium-Metal Batteries. ACS Nanoscience Au, acsnanoscienceau.1c00056, 2022

• highly aligned boron nitride (BN) nanosheets + poly(vinylidene fluoridehexafluoropropylene) (PVdF) polymer----> electrolyte for Li-metal batteries
• safe
• 400% increase in in-plane thermal conductivity ---> fast heat distribution
• suppresion of Li dendite growth

Direct-Ink-Writing of Electroactive Polymers for Sensing and Energy Storage Applications[edit | edit source]

Pinto, R. S., Serra, J. P., Barbosa, J. C., Gonçalves, R., Silva, M. M., Lanceros‐Méndez, S., & Costa, C. M., "Direct‐Ink‐Writing of Electroactive Polymers for Sensing and Energy Storage Applications". Macromolecular Materials and Engineering, 306(11), 2100372, 2021

• Sensors separators: wax or poly(carboxylic acid) alone or with fillers (SiO2,Na2O, or CNT), piezoelectric (should be dense)
  • PVDF
  • PVDF-HFP: a co-polymer of PVDF---> good resistance to solvents, thermoxidative degradation, and hydrophobic stability
• PVDF and copolymer in batteries: polymer binder in anodes and cathodes, seperator membranes (should be porous)
• ---> refer to paper for EXPERIMENTAL

Direct Ink Writing of Moldable Electrochemical Energy Storage Devices: Ongoing Progress, Challenges, and Prospects[edit | edit source]

Zhang, Q., Zhou, J., Chen, Z., Xu, C., Tang, W., Yang, G., Lai, C., Xu, Q., Yang, J., & Peng, C. "Direct Ink Writing of Moldable Electrochemical Energy Storage Devices: Ongoing Progress, Challenges, and Prospects". Advanced Engineering Materials, 23(7), 2100068, 2021

• Refer to the table for proper materials for Direct ink writing (DIW) of energy devices

Direct Ink Writing of Li_1.3Al_0.3Ti_1.7(PO₄)₃-Based Solid-State Electrolytes with Customized Shapes and Remarkable Electrochemical Behaviors[edit | edit source]

Liu, Z., Tian, X., Liu, M., Duan, S., Ren, Y., Ma, H., Tang, K., Shi, J., Hou, S., Jin, H., & Cao, G., "Direct Ink Writing of Li _1.3 Al _0.3 Ti _1.7 (PO ₄) ₃ ‐Based Solid‐State Electrolytes with Customized Shapes and Remarkable Electrochemical Behaviors". Small, 17(6), 2002866. 2021

• All-solid-state batteries
• Li _1.3 Al _0.3 Ti _1.7 (PO ₄) ₃ -based ink electrolyte:
• high conductivity and electrochemical stability
• less sensitive to oxygene---> prepare in air---> low-cost
• electrochemically stable
• Ceramic solid state electrolyte (CSSE):
  • +(DI) water (wetting) and isopropanol (IPA) (dispersing)
  • 950 degree sintering (secondary phase weaker), proper grain size (higher degrees are bigger)
  • LiFePO4 cathode, Li anode
  • high discharge capacity of 150 mAh g−1 at 0.5 C
• Hybrid solid state electrolyte (HSSE):
  • poly(ethylene oxide) (PEO) and lithium bis(trifluoromethane)sulfonimide (LiTFSI)
  • LiFePO4 cathode, Li anode
  • 300 degree decomposition temperature
  • high discharge capacity of 150 mAh g−1 at 0.5 C

Direct Ink Writing advances in multi-material structures for a sustainable future[edit | edit source]

Rocha, V. G., Saiz, E., Tirichenko, I. S., & García-Tuñón, E. "Direct ink writing advances in multi-material structures for a sustainable future". Journal of Materials Chemistry A, 8(31), 15646–15657, 2020

DIW approaches to multi-material structures

• Single-paste cartridge:
• multi-material ink extruded from a single cartridge through a single nozzle
• in situ mixing to change the ratio between two components
• structural control: macrolevel & microlevel
• microstructure: use of flow, external fields to align anisotropic particles
• enhance fracture resistance in ceramics
• 4D printing
• Multiple-pastes cartridges:
• different compositions from different cartridges
• switching of cartridges and/or nozzles
• tip alignment:control of the interface between the extruded lines
• start/stop flow settings: density and rheology of the formulation
• Co-extrusion of pastes:
• print core-shell filaments
• ceramic matrix composites
• cores that are subsequently eliminated to create channels

Recent Progress of Direct Ink Writing of Electronic Components for Advanced Wearable Devices[edit | edit source]

Zhang, Y., Shi, G., Qin, J., Lowe, S. E., Zhang, S., Zhao, H., & Zhong, Y. L, "Recent Progress of Direct Ink Writing of Electronic Components for Advanced Wearable Devices". ACS Applied Electronic Materials, 1(9), 1718–1734, 2019

• Printable inks: fillers, binders, additives and solvents
• microelectrodes, strain sensors, soft robotics and biomedical devices, stretchable wires, stretchable circuits, supercapacitors, piezoelectric nanogenerators
• TABLE: Ink components for several 3D direct ink written wearable devices, including strain sensors, LIBs and nanogenerators.

Reprocessable 3D-Printed Conductive Elastomeric Composite Foams for Strain and Gas Sensing[edit | edit source]

Wei, P., Leng, H., Chen, Q., Advincula, R. C., & Pentzer, E. B. "Reprocessable 3D-Printed Conductive Elastomeric Composite Foams for Strain and Gas Sensing". ACS Applied Polymer Materials, 1(4), 885–892, 2019

• Foams for Strain and Gas Sensing
• Using Direct ink writing (DIW)
• Materials: TPU in DMF ---> capped & stirred on magnetic hot plate at 80 °C for 24 hours---> cooled---> plastic cup---> + CB & nanoclay--->homogenized for 6 min
• 3D printing: ink on glass 0.22 mm height---> then into deionized water for 30 min (remove DMF)---> in HF (3 w%) at room temp for 24 hours---> deionized water ---> freeze dried

Full 3D Printing of Stretchable Piezoresistive Sensor with Hierarchical Porosity and Multimodulus Architecture[edit | edit source]

Wang, Z., Guan, X., Huang, H., Wang, H., Lin, W., & Peng, Z. "Full 3D Printing of Stretchable Piezoresistive Sensor with Hierarchical Porosity and Multimodulus Architecture". Advanced Functional Materials, 29(11), 1807569, 2019

• Stretchable Piezoresistive Sensor by direct ink writing (DIW)
• materials:
• substrate: mixing The base and curing agent of PDMS, degassed
• electrode: dissolving TPU in N,Ndimethylformamide (DMF) solvent in 1:1.5 weight ratio + silver microflakes (mix 30 min)
• sensing layer ink: NaCl particles (ball milling)---> + CB+TPU
• 3D printing:
• substrate with a thickness of about 200 µm--->cured at 80 °C for 2 h---> oxygen plas,a for 2 min
• electrode & sensing layer: high-viscosity ink---> print---> dried at 110 degree---> immersed in water for NaCl removal

A hybrid three-dimensionally structured electrode for lithium-ion batteries via 3D printing[edit | edit source]

Li, J., Leu, M. C., Panat, R., & Park, J. "A hybrid three-dimensionally structured electrode for lithium-ion batteries via 3D printing". Materials & Design, 119, 417–424, 2017

• Direct ink writing (DIW) of electrode
• Materials: 85.5 wt% LMO powder (MTI, 13 μm) + 6.5 wt% carbon black + 8 wt% Polyvinylidene fluoride (PvdF) + N-Methyl-2-pyrrolidone solvent (NMP)---> mixed---> 2000 RMP for 20 min at room temperature
• rheology by viscometer
• 3D printing:
• current collector: Al on a substrate heated to 120 °C
• 200 μm nozzle
• coin cell in argon-filled glove box, LMO used as a cathode, Li foil as an anode, commercial PP/PE/PP seperator, liquid electrolyte 1 M LiFP6 EC:DMC 1:1

3D Printing of Interdigitated Li-Ion Microbattery Architectures[edit | edit source]

Sun, K., Wei, T.-S., Ahn, B. Y., Seo, J. Y., Dillon, S. J., & Lewis, J. A. "3D Printing of Interdigitated Li-Ion Microbattery Architectures". Advanced Materials, 25(33), 4539–4543, 2013

• Direct ink writing (DIW)
• Materials:
• 4.5 g of LTO nanoparticles in 110 mL of deionized (DI) water+ 40 mL of ethylene glycol && 3.0 g of LFP nanoparticles in 80 mL of DI water and 40 mL of EG---> ball milled for 24 h @ room temp & centrifuged-----> in glycerol+ 3.5 wt% aqueous hydroxypropyl cellulose (HPC) + 3 wt% aqueous hydroxyethyl cellulose (HEC)-------> LTO ink: 3 wt% aqueous hydroxyethyl cellulose (HEC) & LFP ink: 20 wt% glycerol, 20 ∼ 30 wt% EG, 8 wt% HPC, 2 wt% HEC, and DI water
• current collector: gold
• ---> print---> annealed @ 600 degrees for 2h in Ar gas (tube furnace)
• Packaging: thin-walled poly(methyl methacrylate) (PMMA) ---> cut---> around microbattery---> sealed with PDMS gel---> cured @ 150 degree
• Liquid electrolyte

3D-Printed Cathodes of LiMn1−xFexPO4 Nanocrystals Achieve Both Ultrahigh Rate and High Capacity for Advanced Lithium-Ion Battery[edit | edit source]

Hu, J., Jiang, Y., Cui, S., Duan, Y., Liu, T., Guo, H., Lin, L., Lin, Y., Zheng, J., Amine, K., & Pan, F. "3D-Printed Cathodes of LiMn _{1− x} Fe _x PO ₄ Nanocrystals Achieve Both Ultrahigh Rate and High Capacity for Advanced Lithium-Ion Battery". Advanced Energy Materials, 6(18), 1600856, 2016

• Direct ink writing (DIW)
• Materials:
• LiMn0.21Fe0.79PO4@C: LiMn0.21Fe0.79PO4: Ferrous sulfate/manganous sulfate, phosphoric acid, and lithium hydrate in mole ratio of 1:1.25:2.7 (FeSO4:MnSO4 = 8:2) + ethylene glycol---> FeSO4/MnSO4 + H3PO4 and LiOH (6 h at 180 degree, N2 gas)----> wash with water & ethanol---> dried at 70 degrees for 6 h in vacuum---> LiMn0.21Fe0.79PO4+ 18.5% glucose and 1.5% ascorbic acid (calcinated at 450 degrees for 2 h and 650 degrees for 6 h in Ar+ C---> LiMn0.21Fe0.79PO4@C+XC-72 carbon black, and PVDF---> 3D print
• seperator: Celgard membrane
• counter electrode and reference electrode: lithium foil
• electrolyte: LiFP6 dissolved in a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and dimethyl carbonate with a volume ratio of 1:1:1
• test: room temp, coin cell, Ar glove-box

3D Printing of Customized Li-Ion Batteries with Thick Electrodes[edit | edit source]

Wei, T., Ahn, B. Y., Grotto, J., & Lewis, J. A. "3D Printing of Customized Li‐Ion Batteries with Thick Electrodes". Advanced Materials, 30(16), 1703027, 2018

• Direct ink writing (DIW)
• Electrodes: active electrode (10 gr LFP or LTO) and conductive KB carbon particle populations are suspended and mixed sequentially in a 1 m lithium bis(trifluoromethane) sulfonamide (LiTFSI)/propylene carbonate (50 gr PC) solution + poly(vinylpyrrolidone) (0.1 gr PVP), at a concentration of 1 wt% with respect to the LFP (or LTO) content (detail in the paper)
• 30 vol% LFP with 1.25 vol% KB and 30 vol% LTO with 1.35 vol% KB in 1 m LiTFSI/PC with 1 wt% PVP% (with respect to LFP or LTO)
• Packaging: UV-curable epoxy and fumed SiO2 (4 vol%)
• Seperator and electrolyte: composed of UV-curable ethoxylated trimethylolpropane triacrylate (ETPTA), Al2O3 particles, electrolyte (1 m LiTFSI/PC), and photoinitiator (thin seperator is desired)
• Test: at 22 degrees with rheometer, Oscillatory measurements (G′, G″), Optical microscopy images, electrochemical experiments (potentioestat, standard galvanostatic), Celgard separator for seperator analisys, Electronic conductivities, Swagelok cell, AC Impedance measurements, Cyclic voltammetry, self-discharge measurement
• Fully 3D print: 1) Glassy Carbon, 2) packaging walls + UV, 3) anode into package, 4) seperator on top of anode+ UV, 5) Cathode, 6) Glassy Carbon, 7) packaging+ UV, 8)UV for whole battery package

3D-Printed MOF-Derived Hierarchically Porous Frameworks for Practical High-Energy Density Li–O2 Batteries[edit | edit source]

Lyu, Z., Lim, G. J. H., Guo, R., Kou, Z., Wang, T., Guan, C., Ding, J., Chen, W., & Wang, J. "3D-Printed MOF-Derived Hierarchically Porous Frameworks for Practical High-Energy Density Li–O2 Batteries". Advanced Functional Materials, 29(1), 1806658, 2019

• Direct ink writing (DIW)
• Materials:
• Co-MOF: 2-methylimidazole solution (C4H6N2, 40 mL, 0.4 m)+cobalt nitrate solution (Co(NO3)2·6H2O, 40 mL, 0.025 m)---> 4 h---> washed with deionized water, and dried
• CP-Co-MOF: carbon paper (CP) collector + solution (?)--->4h--->washed with deionized water, and dried
• 3DP-Co-MOF: Co-MOF + deionized water---> +Pluronic F127 powder (25 wt%) (m = 100, n = 65, molecular weight = 12 500 – 12 600)---> stirred at 4 degrees--->Co-MOF-F127---> refrigerator below 4 degrees for 24-36 h---> 3d print---> dry in room temperarure for 24 h
• Tests:
• XRD, TEM, Raman, XPS, N2 adsorption/desorption isotherms
• specific surface area: Brunauer–Emmett–Teller
• pore volume: Barrett–Joyner–Halenda
• macropore size: Quantachrome 3GWin2 porosimetry
• resistance (R): Fluke 2638A Hydra Series III Digital Multimeter
• electric conductivity (σ): σ = L/(R × A)
• Ink rheology: Discovery Hybrid Rheometer
• apparent viscosity: as a function of shear rate using logarithmically ascending series
• elastic storage and viscous loss: oscillatory mode as a function of controlled shear stress (102 – 106 Pa) at a frequency of 6.28319 rad s−1
• Coin cells (2032): Li metal foil (counter electrode), glass fiber (seperator), LiClO4-DMSO (electrolyte)

Environmentally Friendly Lithium-Terephthalate/Polylactic Acid Composite Filament Formulation for Lithium-Ion Battery 3D-Printing via Fused Deposition Modeling[edit | edit source]

Environmentally Friendly Lithium-Terephthalate/Polylactic Acid Composite Filament Formulation for Lithium-Ion Battery 3D-Printing via Fused Deposition Modeling—IOPscience. (n.d.). Retrieved July 3, 2022

• FDM is a solvent-free method
• lithium-terephtalate/polylactic acid (Li2TP/PLA): negative electrode + poly(ethylene glycol) dimethyl ether as plasticiser + carbon black for enhancing electrical performance
• Materials:
• lithium terephthalate (Li2TP): 60.0 g of terephthalic acid + 250 ml of ethanol + 31.8 g of LiOH∙H2O ---> stirred overnight at room temperature---> precipitation---> wash with ethanol---> dry--> vacuum at 150 degrees
• Filament: Li2TP+ Carbon black (4:1) ---> ball-mill for 15 min---> + PLA---> milling for 15 min---> + PEDGME500 plasticizer ---> result: PLA:Li2TP:CB:PEGDME500 equals to 40:40:10:10
• Extruder temp is 180 degrees
• 3D printing:
• 30 °C higher than the melting temperature with 60 degrees bed temp
• Tests:
• Differential scanning calorimetry (DSC)
• Thermogravimetric analysis (TGA)
• Transmission infrared analysis (FTIR)
• Nuclear magnetic resonance (NMR)
• Atomic absorption spectroscopy (AAS)
• Electrochemical impedance spectroscopy
• AC impedance measurement
• Conductivity: σ=1/R*d/A (d electrode thickness, A electrode surface area, R respective resistances)
• Electrochemical characterization: Swagelok-type cells, Metallic lithium (counter/reference electrode for halfcells), 3D printed electrode: working electrode, Fiberglass separator, LiPF6 in ethylene carbonate and diethyl carbonate (EC:DEC 1:1 weight ratio) liquid electrolyte

3D Printed Nanocarbon Frameworks for Li-Ion Battery Cathodes[edit | edit source]

Gao, W., & Pumera, M. (2021). 3D Printed Nanocarbon Frameworks for Li‐Ion Battery Cathodes. Advanced Functional Materials, 31(11), 2007285, 2021

• 3D printed electrodes: accommodate the volumetric change during Li-ion insertion and extraction for improved long-term cyclability.
• FDM: low cost, high efficiency, simplicity and easily accessible large size capability with high precision.
• thermoplastic filaments challenges: obstacle electrochemistry properties---> carbon black, graphite should be added into thermoplastic polymer ---> still not satisfiying---> post-treatment is needed (removal of insulating thermoplastics): dissolution, chemical saponification reaction with strong alkaline solutions, electrochemical degradation or pyrolysis
• thermoplastic filaments advantages: as a binder, mechanical stability
• 0D carbon-based filament for cathode: low-cost but less conductive---> higher loading is required
• solution: surface engineering (deposition of conductive materials on the surface of 3D-printed electrodes)
• Al is proper as current collector: electrical conductivity, light weight, and cost efficiency BUT is prone to corrosion in aqueos electrolyte---> coating Al
• high-performance electrodes: conductive polymer-coated surfaces--->protective layer, mechanical properties, conductive----> conductive poly(ortho-phenylenediamine) (PoPD) replace at PLA places after removing
• electrode: filament (PLA+ 0D carbon)---> print---> remove PLA---> add PoPD---> add LMO
• Materials:
• framework: 3d print of commercially available conductive carbon filament at 215 nozzle temp and 60 bed temp----> immerge in dimethylformamide (DMF) for 1---> rinsed with ethanol and deionized water---> electrodeposition of PoPD (5mM oPD monomer (1,2-diaminobenzene), 0.1 M H2SO4 (95–98%), Pl as current collector)---> deionized water
• 3D@PoPD@LMO electrode: LMO + PVDF+ carbon black (8:1:1) in NMP---> 1h--->drop-coated on PoPD-refilled 3D frameworks
• TESTs:
• SEM, EDX, XPS
• Electrochemical activity on the surface: electrolyte containing 10 mm [Fe(CN)6]4−/3− and 0.1 m KCl
• Electrochemical impedance spectroscopy (EIS)
• FUTURE work: using other conductive polymers

A Simple, Low-Cost Conductive Composite Material for 3D Printing of Electronic Sensors[edit | edit source]

Leigh, S. J., Bradley, R. J., Purssell, C. P., Billson, D. R., & Hutchins, D. A. A Simple, Low-Cost Conductive Composite Material for 3D Printing of Electronic Sensors. PLOS ONE, 7(11), e49365, 2012

• conductive Carbon Black (CB) filler
• "carbomorph" Filament:
• 3 g of the polymorph thermoplastic +carbon black+40 ml of dichloromethane---> 1 h stirred---> eveporate---> water bath at 80 degrees for 1 min---> rolled between 2 glass plates till 3 mm wide filament---> cooled for 2 h
• 3d printed by PLA setting!

Molecular Engineering of Biorefining Lignin Waste for Solid-State Electrolyte[edit | edit source]

Li, Q., Cao, D., Naik, M. T., Pu, Y., Sun, X., Luan, P.,... & Zhu, H. Molecular Engineering of Biorefining Lignin Waste for Solid-State Electrolyte. ACS Sustainable Chemistry & Engineering, 2022

Lignocellulosic biomass:

• cellulose+ hemicellulose+ lignin
• polysacchrides (cellulose and hemicellulose)---> pretreated & hydrolyzed---> biofuel---> lignin waste
• lignin: waste of paper industry and biorefineries.
• solid-state electrolytes (SSEs) (which also work as seperator): solid ceramic/glass electrolyte (SCE), solid polymer electrolyte (SPE), and composite polymer electrolyte (CPE).
• CPE: ionic conductivity, remarkable flexibility, high processability, and mechanical robustness
• Poly(ethylene oxide) (PEO):
• soft polymer, good Li ionic conductivity, limited film formability and poor thermostability, poor mechanical performance and durability

Lignin:

• aromatic moieties & aryl ether (β−O−4)---> disassociation and conduction of Li ions
• heterogeneous--->thermostability but poor formability for film processing, poor ionic conductivity
• Bond PEG and lignin---> PEG-g-lignin polymer: excellent Li ionic conductivity, good thermostability, and good film formability
• Types of electrolytes: SPE (composed of PEG-g-lignin with the addition of different amount of PVDF-HFP to improve the film formability), CPE (composited by LLGZO ceramics and PEG-g-lignin that have been infiltrated into a polytetrafluoroethylene (PTFE))
• Lignin & PVDF-HFP---> NOT conductive

Materials:

• Lignin from LignoBoost process, PTFE film, PEG (MW 200 g/mol), LiTFSI, gallium doped lithium lanthanum zirconium oxide (LLGZO, Li6.4Ga0.2La3Zr2O12), PVDF-HFP

Synthesis of PEG-g-lignin:

• 60 g of LignoBoost lignin---> dried---> + 300 g of PEG and 0.9 g of 95% H2SO4---> 160 °C using an oil bath for 4-h---> into deionized water ---> centrifugation and lyophilization

SPE:

• 300 mg of PEG-g-lignin + PVDF-HFP (50 w%, 30 w%, and 15 w %as per PEG-g-lignin)---> mix---> N,Ndimethylformamide (DMF)---> 20 w %. Lithium salt (LiTFSI)---> cast---> dried at 80 degrees

CPE:

• PEG-g-lignin/PVDF-HFP/LiTFSI+ LLGZO powder (1:3)---> mixed---> into PTFE film

TESTS:

• FT-IR (the structure of PEG-g-lignin), P nuclear magnetic resonance (P NMR) (grafting of PEG onto lignin), 2D HSQC NMR (The change of lignin linkage), Gel permeation chromatography (GPC) (changes in the molecular weight of lignin), Thermogravimetric analysis (TGA) (thermostability), differential scanning calorimetry (DSC), AC impedance

Lignin biopolymer: the material of choice for advanced lithium-based batteries[edit | edit source]

Baloch, M., & Labidi, J, Lignin biopolymer: The material of choice for advanced lithium-based batteries. RSC Advances, 11(38), 23644–23653, 2021

Basic of electrochemical energy storage systems:

• Inorganic and/or rare metal electrodes (Mn, Co, Ni and Fe), polymeric binders (such as PVDF mixed with toxic NMP solvents), and volatile non-aqueous electrolytes (organic carbonates such as DMC and DEC, or ethers such as DME and DIOX) ---> expensive, toxic
• Organic compounds: high power energy storage application, poor ionic and electrical conductivity
• Lignin: cheap carbon source, abundant, high charge density, �50,000,000 tons each year, amorphous polymer, high cabon content, bio-degradability, antimicrobial behaviour, adhesive properties, thermal stability, additive properties, dust dispersant and blending properties, high mechanical strength, rigid
• Based on plant, extraction method and experimental condition---> different functionality
• Hydrolysed lignin: cathode
• organosolv lignin and acetone lignin: Anode
• Kraft lignin: cathode and binder
• Quinone: facilitate a fast and reversible two electron/proton redox reaction ---> solubility of quinone electrode in the electrolyte solvents ---> poor cycle life and performance
• LS lignin with polypyrrole (PPY/LS)---> electrode ---> poor cyclic stability
• 3,4-ethylenedioxythiophene (EDOT)---> PEDOT/LS hybrid material electrode---> better cyclic stability
• Primary battery CATHODES: Hydrolysed lignin, sun flower-derived lignin, buckwheat-derived lignin

CATHODE in Li-ion batteries:

• Lignin/PEDOT (20/80) + conductive carbon

Gel polymer ELECTROLYTES (GPEs):

• polyacrylonitrile (PAN), polyvinyl acetate (PVA), polyvinylidene fluoride (PVDF), and polyethylene oxide (PEO)---> not biodegradable---> white pollution----> use lingin-based GPE---> poor mechanical properties---> use PVP/lignin

ANODE:

• Lignin + PLA + TPU---> porous
• Pyrolise of Lignin with Si---> carbon-coated silicon (Si@C)
• CATHODE in Li-O2 batteries: Lignin as activated carbon with KOH or H3PO4---> high efficiency low-cost

Bio-derived carbon nanofibers from lignin as high performance Li-ion anode materials[edit | edit source]

Culebras, M., Geaney, H., Beaucamp, A., Upadhyaya, P., Dalton, E., Ryan, K. M., & Collins, M. N. Bio‐derived Carbon Nanofibres from Lignin as High‐Performance Li‐Ion Anode Materials. ChemSusChem, 12(19), 4516–4521, 2019

• Anode in Li ion batteries: low energy density---->graphene, carbon nanotubes and mesoporous: high cost & difficult to make by conventional methods
• Carbon nanofiber (CNF): electrospinning using PAN as carbon precursor: lower cost rather than CNT but high production cost, high CO2 emissions, solvent usage during synthesis----> Lignin instead of PAN: low viscosity---> blend with TPU (provide miscible blend) and PLA (provide porous structure)+ methylene diphenyl diisocyanate (MDI) as crosslinking agent

Solution and CNF preparation:

• PLA+ THF:DMF (1:1 v/v) 1 hour at 50 degrees & TPU+ DMF 1 hour at 50 degrees---> Lignin in each solvent, stirring for 30 min at 50 degrees---> +7% MDI stirring for 5 min at 50 degrees---> electrospinning

3 steps: product, stabilised, and carbonised

TESTS:

• SEM, EDS, FTIR, attenuated total reflectance accessory (ATR), Raman, two electrode Swagelok type cells, SETARAM TG-DTA 1600, Brunaeur-Emmett-Teller (BET)

Lignin-Based Materials for Sustainable Rechargeable Batteries[edit | edit source]

Jung, H. Y., Lee, J. S., Han, H. T., Jung, J., Eom, K., & Lee, J. T. Lignin-Based Materials for Sustainable Rechargeable Batteries. Polymers, 14(4), 673, 2022

• Seperator: PP & PE---> poor thermal stability and ion conductivity----> Lignin: thermal stability, ionic conductivity, and mechanical strength----> fabricated by electrospinning: lignin–PVA, lignin–PAN, lignin nanoparticle (LNP) coated on a conventional separator
• Electrolyte: Lignin offers ion conduction paths and suppression of the lithium dendrite formation
  • lignin– polyvinylpyrrolidone (PVP) gel + silanol and PVP to the neutralized alkaline lignin slurry (as electrolyte & seperator)
  • lignin–linear poly(N-vinyl imidazole)-copoly(poly(ethylene glycol) methyl ether methacrylate) copolymer (LCP) gel: film-forming capability, promising electrochemical performance, and good solubility in water
• Anode: pyrolise in Lignin---> carbon structure
  • alternative for PAN---> prepared by electrospinning or melt-spinning
  • complementary carbon source= cellulose acetate (CA) + kraft lignin
  • Softwood lignin---> hard to extrude
  • Hardwood---> easy to extrude
  • coprecipitation of Si/lignin---> anneal---> Si-nanoparticle-loaded carbon particles (high efficiency anode material)
  • Nitrogen-doped lignin-based carbon
• Cathode: Lignin + Conductive polymers
  • lignin/PEDOT electrode with a 20/80 mass ratio in LIB or NIB
  • NH4F, Al2(SO4)3, KMnO4, Lignin ---> nanowires in ZIB

Hybrid biopolymer electrodes for lithium- and sodium-ion batteries in organic electrolytes[edit | edit source]

Navarro-Suárez, A. M., Carretero-González, J., Casado, N., Mecerreyes, D., Rojo, T., & Castillo-Martínez, E. Hybrid biopolymer electrodes for lithium- and sodium-ion batteries in organic electrolytes. Sustainable Energy & Fuels, 2(4), 836–842, 2018

• Lignin-based cathode---> Lignin:EDOT cathode using Iron (III) Chloride as catalyst and Sodium Persulfate as primary oxidant
• electrochemical test by Li foil as anode
• lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6) as electrolyte

Carbon nanofibers bridged two-dimensional titanium carbide as a superior anode in lithium-ion battery[edit | edit source]

Lin, Z., Sun, D., Huang, Q., Yang, J., Barsoum, M. W., & Yan, X. Carbon nanofiber bridged two-dimensional titanium carbide as a superior anode for lithium-ion battery. Journal of Materials Chemistry A, 3(27), 14096–14100, 2012

• interlayar stack in Mxene---> decreases the electrical conductivity----> using CNF as bridge
• Ti3C2Tx---> hydrophilic---> host for cations
• Ti3C2Tx---> temp 600 degrees ---> Ti3C2
• method: Co catalyst (Co(NO3)2)+ PVP (prevent agglomeration) in Ti3C2Tx---> dried---> growing CNF through CVD
• Ti3C2-CNF-1-15---> best ratio
• TEST: SEM, TEM, XRD, Brunauer-EmmettpTeller (BET), cyclic voltammetry (CV), galvanostatic, charge-discharge (GCD) cycling, electrochemical impedance spectroscopy (EIS)

Low Cost Synthesis Method of Two-Dimensional Titanium Carbide MXene[edit | edit source]

Rasid, Z. A. M., Omar, M. F., Nazeri, M. F. M., A'ziz, M. A. A., & Szota, M. Low Cost Synthesis Method of Two-Dimensional Titanium Carbide MXene. IOP Conference Series: Materials Science and Engineering, 209, 012001, 2017

• MAX phase---> remove A layer by etching
• Pressureless sintering (PLS)---> low cost to synthesize a MAX phase
• Materials:
• titanium hydrate (TiH2)+ Al+ Graphite (3:1.1:2)---> ball mill---> (Ti3AlC2+ hexagonal graphite+tetragonal TiO2+cubic TiC)---> cold-press (6000 psi)---> sinter in 1350 degrees for 2 h---> in hydrofluoric solution (HF) for 20 h---> centrifuge---> wash (pH 7)---> methanol---> dried

3D printing of lignin: Challenges, opportunities and roads onward[edit | edit source]

Ebers, L.-S., Arya, A., Bowland, C. C., Glasser, W. G., Chmely, S. C., Naskar, A. K., & Laborie, M.-P. 3D printing of lignin: Challenges, opportunities and roads onward. Biopolymers, 112(6), e23431, 2021

• Hardwood lignin: linear and less branched, lower softening temperature
• Thermal degredation in lignin is 150 to 170 degrees

FDM: (up to 40% lignin loaded is investigated)

• native hardwood lignins of low molecular weight and low Tg
• ABS+ lignin+ nitrile rubber or polyoxyethylene---> tough and strong
• nylon+ lignin+carbon---> stiffnss, strength, ready to heat
• ligning + nitrile rubber---> toughness and yield stress & high tensile strength but hard to print due to high molecular weight rubber component and its crosslinking with lignin---> + polystyrene
• organosolv hardwood lignin + PLA ---> excellent printability with FDM (15 wt %)

DIW: (proper for lignin printing)

• cellulose nanofibers (CNF), alginate & colloidal lignin+ Ca2+ ions crosslinking
• Soda lignin + Pluronic F127---> print & freez dried, oven cured
• hydroxypropyl cellulose (HPC) + organosolv lignin (OSL) in acetic acid---> thermal post processing with citric acid and a dimerized fatty acid

SLA:

• Kraft lignin+methacrylate resin with solution blending procedure
• acylation of organosolv lignin using methacrylic anhydride allowed up to (15 wt %) lignin to be incorporated into an open-source SLA resin---> with 10 wt% lignin affording two times the ultimate tensile strength and a 3-fold increase in strain at break
• lignin is useful as a photoinitiator

Lignin: A Biopolymer from Forestry Biomass for Biocomposites and 3D Printing[edit | edit source]

Tanase-Opedal, M., Espinosa, E., Rodríguez, A., & Chinga-Carrasco, G. Lignin: A Biopolymer from Forestry Biomass for Biocomposites and 3D Printing. Materials, 12(18), 3006, 2019

• Lignin: highly abundance, low-cost and biodegradability, high carbon content, high aromaticity, and reinforcing capability
• Extracting lignin by soda process: using NaOH, Ca(OH)2) to solubilize or depolymerize lignin, and make lignin extractable from biomass matrix, environmentally friendly
• Soda lignin: sulphur-free, without odour and with a chemical composition closed to pure lignin
• FDM filament: organosolv hardwood lignin+ABS, kraft softwood lignin + PLA, Soda+PLA

Materials:

• Soda lignin+ PLA

Lignin extraction:

• Norway sptuce by soda process with MK circulation reactor

Lignin Precipitation:

• adding sulphuric acid---> change in color and viscosity---> centrifuge

Filament:

• PLA+ lignin (20 & 40%)---> extrude twice in 200, 205 and 210 degrees---> FDM in 200, 205 and 210 degrees

Tests:

• TGA, DSC, SEM, mechanical testing (tensile testing), FTIR, XRD
• mechanical strength is proper for 215 degrees sample, good antioxidant activity

Lignin-based electrodes for energy storage application[edit | edit source]

Liu, H., Xu, T., Liu, K., Zhang, M., Liu, W., Li, H., Du, H., & Si, C. Lignin-based electrodes for energy storage application. Industrial Crops and Products, 165, 113425, 2021

• Lignin: low cost, high carbon content, plentiful functional groups
• Lignin found in: softwoods contain more lignin (25–35 %), hardwoods contain medium lignin (20–25 %), and gramineae plants contain less lignin (15–25 %)
• lignin classified into: alkali lignin (AL), kraft lignin (KL), lignosulfonate (LS), enzymatic hydrolysis lignin and organic solvents fractionated lignin
• Supercapacitors: 1)electric double layer capacitors (EDLC): energy storage between between the electrode and the electrolyte, 2) pseudocapacitors (PC): on or near the surface of the electrode
• Carbon content in lignin: more than 60%
• CF for electrode e.g. for EDLC: PAN+Lignin--> electrospinning--> thermal stabilization, carbonization, activation by CO2
• CF for electrode e.g. for EDLC: polyethylene glycol lignin (PEGL)---> activated carbon fibers & soda lignin (SL)---> activated carbon fibers
• Lignin-base activated carbon:
• 1) physical activation: carbonization and activation: with CO2 or O2
• 2) chemical activation: (simultaneous carbonization and activation) --->lignin-based char is mixed with chemical activating agents (ZnCl2, alkali metal compounds (e.g. KOH, K2CO3, Na2CO3) and H3PO4) followed by heating the mixture under an inert atmosphere
  • KOH as activating agent + humidified N2 in microwave--->lignin-based porous carbon (LPC)
  • enzymatic hydrolysis lignin--->hydrothermal carbonization---> KOH/Ca(OH2)---> lignin-based porous carbon (LPC)

Recycling of Lignin and Si Waste for Advanced Si/C Battery Anodes[edit | edit source]

Liu, W., Liu, J., Zhu, M., Wang, W., Wang, L., Xie, S., Wang, L., Yang, X., He, X., & Sun, Y. Recycling of Lignin and Si Waste for Advanced Si/C Battery Anodes. ACS Applied Materials & Interfaces, 12(51), 57055–57063, 2020

• Silicon waste of photovoltaic industry (∼40 wt % (∼1.54 × 105 tons)) & Lignin waste of paper industry (7.0 × 107 tons annually from the pulp industry)
• Si: poor electronic conductivity & huge volume variation of Si
• Si in C matrix: low cost, user friendly, prevent Si volume change and enhance conductivity
• cationic surfactant cetyltrimethyl ammonium bromide (CTAB)-modified Si particles + electronegative lignin molecule

Material:

• Solar waste silicon powder---> ball milling for 20 h ---> wash with 10 wt % HF solution and DI water---> 40 mg in 40ml DI water with 90 mg CTAB---> sonicated and stirred for 30 min
• Lignin from soda pulping black liquor---> 400 mg + 40 ml KOH---> stirred---> + silicon dispersion ---> Si/CTAB+Lignin---> 500 μL of sulfuric acid ---> Si/lignin collected by centrifugation and washed with deionized water (3 times)---> dry at 60 degree in vaccum one night---> anneal at 800 degrees for 2 h---> Si/C

TESTS:

• FESEM (morphology), TEM (microstructure), XRD, FTIR & XPS (chemical composition), TGA
• electrochemical test:
• Si/C---> slurry cast on Cu (80 % Si/C+ 10 % binder (poly(acrylic acid))+ 10 % conductive additive (super P)

Lignin/Si Hybrid Carbon Nanofibers towards Highly Efficient Sustainable Li-ion Anode Materials[edit | edit source]

Culebras, M., Collins, G. A., Beaucamp, A., Geaney, H., & Collins, M. N. Lignin/Si Hybrid Carbon Nanofibers towards Highly Efficient Sustainable Li-ion Anode Materials. Engineered Science, Volume 17(0), 195–203, 2022

• Fabricating an anode through electrospinning of lignin/PLA/Si---> PLA provides pores in lignin (CNF) and Si particles distribute homogeneously in fibers

Materials:

• Organosolv hardwood lignin, PLA, DMF, MDI, Si, Super P, carbon black, 1.0 M LiPF6 in EC-DEC (1:1 v/v) electrolyte, vinylene carbonate (VC, 97%)

Solution:

• PLA in THF:DMF ---> stir for 1 h at 60 degrees---> +lignin---> mix for 30 min---> +Si---> mix for 10 min---> sonicate for 20 min---> +MDI---> electrospun

CNF:

• electrospun---> stabilize: 25 to 150 by 1 degree per min---> keep at 150 for 14 h---> 150 to 200 by 1 degree per min---> keep at 200 for 1 h---> 200 to 250 by 1 degree per min---> keep at 250 for 1 h---> carbonize: tubular furnace---> room to 900 degrees by 10 degrees per min under N2 flow---> 900 for 30 min

Electrode slurry:

• Carbon black in 1.5 wt% CMC in H2O---> stirred for 6 h---> +CNF---> stirred overnight---> doctor blade at 60 degrees

TESTS:

• SEM, EDX, FESEM, Raman spectra, XRD, XPS, electrochemical test

A review of 4D printing[edit | edit source]

Momeni, F., M.Mehdi Hassani.N, S., Liu, X., & Ni, J, "A review of 4D printing". Materials & Design, 122, 42–79, 2017

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