Silicon Carbide Nanoparticles as a Mechanical Boosting Agent in Material Extrusion 3D-Printed Polycarbonate[1][edit | edit source]
- DIW of SiO at C/graphite.
3D printer info and variables | DIW | nozzle: ID 260-610 micro | Thickness: 418 (2 layers), 692 (3), 806 (4), 1050 micrometer | Mass loading: 39.2, 60.9, 84.2 mg/cm2 | weight ratio of SiO/graphite, MWCNTs, and binders: 70/20/10 | extrusion speed: 40% | scanning velocity: 8 mm/s | layer thickness: 0.2 mm | 269 micrometer line width by 24G nozzle tip, thickness 418 micrometer | Comb-like design | ||
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Equipment | Ultrasonic | Magnetic stir | vacuum | |||||||||
Material | Current collector: foam Al and Cu | electrolyte: 1.0 M LiPF6 EC: EMC. DEC ¼ 1:1:1 + 2% FEC | cathode: LFP | |||||||||
Steps | Ink preparation | 3D printing | vacuum Freeze-drying | |||||||||
TESTS | half cell electrochemical (Li-foil) | Full cell with LFP | apparent viscosity/ shear rate for ink | rate performance (specific capacity/cycle number) | Areal capacity | impedance spectroscopy | charge/discharge | Ragone plot between areal energy density and power density | storage modulus and loss modulus/ shear stress for ink | SEM | EDS | mercury intrusion porosimetry (porosity, pore size, and distribution) |
Results | Areal capacity: 17.9, 26.7, 32.2 mAh /cm2 (respectively with thickness (mass loading)) | Solid content of the ink: 40% is preferable | Porosity: 50-200 nm (nano scale) | Porosity: 1-3 micrometer (micro scale) | Porosity: 100-300 micrometer (macro scale) | 20% of MWCNT is prefarable | 269 micrometer line width by 24G nozzle tip, thickness 418 micrometer are preferable (276 mAh/g @ 3 C specific capacity) | Mass loading of 806 thickness which is 84.3 mg/cm2 is preferred |
A 3D-Printed, Freestanding Carbon Lattice for Sodium Ion Batteries[2][edit | edit source]
- Na battery fabrication with SLA
- pyrolysis
- SLA of hard carbon microlattice then pyrolysis---> Increasing the mass loading --> increasing the energy density and compacting the battery size
3D printer info and variables | mass loading 98 mg cm−2 | beam lengths and widths: 400-133 | x and y pixel resolution of 50 µm | 50 µm thick pattern layer | lattice architecture | 70% in x -75% in y shrinkage after pyrolysis | (x,y) = (119.9, 32.8) for 400-133 after the pyrolysis | resolution= 50 µm | UV exposure time= 35 s for the first layer, 2s for the rest | retraction velocity of the platform= 80 mm/ min | ||||||||
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Design | lattice architecture | |||||||||||||||||
Equipment | LCD-SLA 3D printer | fused quartz tube | ||||||||||||||||
Material | Photocurable resin (phenolic epoxy resin and methacrylate monomer) | 2-propanol | cathode: Na metal foil | electrolyte: 1.0 m NaPF6 in PC | separator: glass fiber filter | binder: PTFE (or PVDF, but it is reported that PTFE is better) | ||||||||||||
Steps | material preparation | 3D print | immerse the electrode in 2-propanol for 3h | dry in ambient condition | first pyrolyzed at 400 for 4h, then 1000 for 4h | 2032 coin-type cell | ||||||||||||
TESTS | Raman spectrum | energy-dispersive X-ray spectroscopy | Charge/ discharge | rate performances | SEM | XRD | calculation diffusion coefficient | |||||||||||
Results | extraordinary high areal capacity of 21.3 mAh cm−2 at 98 mg/ cm^2 | low crystallinity so we have hard carbon | 70% in x -75% in y shrinkage after pyrolysis | bigger graphite that has more space to store Na ions | Coulombic efficiency of 80% in first cycle | increased capacity as the micro structure becomes finer | the overpotential reduces as the micro structure becomes finer | the rate performance improved as the micro structure becomes finer | better capacity as the micro structure becomes finer | the beam width should be as fine as possible | the beam density can be as dense as possible | stable over long term cycling | the total capacity just decreased at the 2nd cycle and no additional lost to 100th cycle | the more mass loading, the more areal capacity | the Na efficiently utilized the entire mass regardless the thickness | increasing the mass loading in conventional method, reduces the areal capacity | shortening the diffusion pathway |
3D printed silicon-few layer graphene anode for advanced Li-ion batteries[3][edit | edit source]
- 3D printing of batteries -->controlling the design & increasing the energy storage
- FDM printing of Si-based anode using PLA as matrix, carbon black-doped polypyrrole and graphene as conductive and Si nano particles as active materials.
- pores inside the 3D printed anodes --> helps the Si to accommodate the volume change during lithiation and delithiation.
3D printer info and variables | FDM | nozzle: 0.4 mm | Nozzle and bed temp: 210- 60 degrees | printing speed: 40 mm / s | Infill density: 100% | Design: electrode with diameter 1 cm, thickness 0.2 mm | |||||||||||
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Equipment | Ultra Centrifugal Mill | Mechanical stirrer | Planetary mixer | A twin-screw extruder | |||||||||||||
Material | Current collector: | electrolyte: Solvionic, 1 M LiPF6 in dimethyl carbonate, DMC : ethylene carbonate, EC 1 : 1 v/v | counter electrode: Li metal | Si nanoparticles (100 nm) | Graphene powder | PLA pellets | cunductive: Carbon black-doped PPy | Separator: Whatman borosilicate | |||||||||
Steps | powdering PLA using Ultra Centrifugal Mill | Dry at 85 degree one night | planetary mixing of PLA, Si, Graphene and carbon black (70wt%, 16, 3, 11) | Extrude a 1.75 mm filament with 175-205 degrees temp | |||||||||||||
TESTS | TEM | SEM | EDX | TGA | tensile tests (by Instron Dual Column Tabletop Universal Testing System) | EIS in 0.02 V voltage amplitude, 0.01- 200 kHz frequency | XRD | Raman spectra | electrical conductivity (Loresta-GX MCP-T700) | Biologic battery tester (0.1-2 V), 20-50 mA/g, CV scan rate: 0.1 mV/s | Specific capacity | Charge/discharge | Rate capability | Long-term cyclic performance and coulombic efficiency | Nyquist plots | cyclic voltammetry (CV) | Gravimetric and volumetric capacities |
Results | Capacity retention: 96% after 350 cycles | specific capacity: 345 mAh / g at 20 mA/g current density |
DLP printing of a flexible micropattern Si/PEDOT:PSS/PEG electrode for lithium-ion batteries[4][edit | edit source]
(great source to link other sources for the introduction)
- free standing 3D printed Si/ PEDOT:PSS/ PEG electrode for Li-ion batteries with DLP.
- The purpose: maximizing the energy storage and minimizing battery weight
- The results: structural integrity and flexibility
- Li ion batteries Advantages: high efficiency, rechargeability, high energy density, small weight, portability
- 3D printing of battery Advantages: complex shapes, control the geometry and architecture--> the same properties inside the architecture like the surface
- SiC Advantages: ultrahigh theoretical capacity and low potential for Li uptake.
- SiC Disadvantages: changes in volume during charging and discharging
- Pulverizing the Si -->form a solid layer at the electrode/ electrolyte interface---> Li dendrites because of the in-homogeneous deposition of Li ions.---> penetrate to the seperator---> short out the cell---> safty issues.
- creating SEI --> electrolyte over-consumption ---> low CE & poor cycling stability.
3D printer info and variables | DLP printing | Distance 0.04 mm between patterned lines | the fisrt electrode diameter: 15.5 mm
after drying: 14 mm |
30% of Si load | honeycomb design | width of line is 50 mm | 200 micrometer laser spot diameter | UV wavelength 375 nm | resolution 75 micrometer | the active material loading in the electrode is 4.2 mg/cm^2 | |
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Equipment | |||||||||||
Material | solid PEDOT:PSS | Si NPs | PEG | Li current collector | |||||||
Steps | 7 mL of water and EG (8:1) + 70 mg of PEDOT:PSS+0.3 g Si NPs | Sinication of the solvent for 20 min | Add BAPO and photoinitiator | Stir over night | PEF/Si/PEDOT:PSS (60/20/5) | 3D print | Dry in a vacuum at 80 degrees for 8 hours | Preparing conventional electrode for comparison (70 Si, 10 carboxymethyl cellulose as binder, 20 acetylene black as conductive agent) | doctor blade the conventional electrode on the Cu foil and dry at 80 degrees) with 20 micrometer thickness and the actice material is 2.2 mg/cm^2 | ||
TESTS | SEM | Viscosity | DSC-TGA | Charge/ discharge | Nyquist plots | ||||||
Results | specific discharge capacity of 1658.4 mA h g-1 | capacity fade of 0.3% per cycle at 800 mA/g current density after 125 cycles | load of 4.2 mg cm-2. | 300 micrometer distance from SI nano particles | From SEM: dispersion of Si, and the position that they are on the surface | From TG: 3 peaks: PEG desorption, PEDOT:PSS thermal decomposition, Si oxidation | charge (discharge) capacity of 1539 (1783) mA h/ g | improved CE of 86.3% | no reduction of charge/ discharge after 125 cycles | reversible capacity of 1105 mA h g-1 |
Synthesis of SiC Resin for 3D Printing of SiC Ceramics by Digital Light Processing[5][edit | edit source]
(for choosing photoinitiator)
- SiC resin + Tethon's high load Genesis & different loads: 10, 20, and 30 % .
- the low viscosity --> DLP print of further than 30 percent (even 50 percent)
3D-printed electrically conductive silicon carbide[6][edit | edit source]
(for choosing photoinitiator and dispersant)
- vat photopolymerization -->fabricate high electrical conductive
- low thermal conductive, and high thermal stable SiC.
3D printer info and variables | vat photopolymerization | layer thickness 0.05 mm | |||||||||
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Equipment | sonicator | ||||||||||
Material | porous silica | Poly (ethylene glycol) diacrylate (PEGDA) | graphene | Photoinitiator: Phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide | Light absorber: 2-Nitrophenyl Phenyl Sulfide | Dispersing agent:
Darvan 811 |
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Steps | Ink | 3D printing | heat treatment | CHaracterization | |||||||
TESTS | SEM | TEM | XRD | Barrett-Joyner-Halenda (BJH) | stress-strain behavior | current-voltage | TGA | ||||
Results | amorphous below 1400 pyrolysis temp |
Additive manufacturing of SiBCN/Si3N4w composites from preceramic polymers by digital light processing[7][edit | edit source]
(for choosing photoinitiator)
Material | Preceramic polymer:
polyborosilazane (PBSZ) |
photo polymerization reactive: trimethylolpropane triacrylate (TMPTA), | Photoinitiator: IRGACURE 819 | dispersant: ??? (not mentioned what) | Si3N4 whiskers |
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3D printing of multicolor luminescent glass[8][edit | edit source]
(for choosing photoinitiator)
- Steriolithography of luminescent transparent glass
- After printing-->immersing the part in ethanol solutions for 15 min -->drying at 60 degrees, sintering at 1250 for 3h.
Material | Preceramic polymer:
polyborosilazane (PBSZ) |
photosensitive monomer: 28.1 wt% HEMA (2-Hydroxyethyl methacrylate) | plasticizer: 14.5 wt% diethylphthalate | crosslink agent: 3.7 wt% PEGDA 200 | 53.7 wt% amorphous silica | photo initiator: 0.4 wt% DMPA | poly(ethylene glycol) diacrylate 200 (PEGDA 200) | diethyl phthalate (99.5%) | 4-methoxyphenol (MEHQ, 99%) | 2,2-dimethoxy-2-phenylacetophenone (DMPA, 99%) | photo absorber: 0.2 wt% Tinuvin 1130 |
Thermo-mechanical and swelling properties of three-dimensional-printed poly (ethylene glycol) diacrylate/silica nanocomposites[9][edit | edit source]
(for choosing photoinitiator)
Material | main resin: poly (ethylene glycol) diacrylate | photoinitiator PL-TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide |
PEGA+ photoinitiator+ SiO2 | ultrasonicated for 30 min |
Synthesis and characterization of hybrid silica/PMMA nanoparticles and their use as filler in dental composites[10][edit | edit source]
(For choosing dispersant)
- CTAB: dispersion material for dispersing Si in PMMA (ionic interaction between positively charged CTAB and negatively charged Si particles ---> forming a hydrophobic interphase --> improving the dispersion of nanoparticles in water & diffusing MMA monomers into the hydrophobic layer--> form a shell.
- adding Si to aqueous CTAB at 2% --> stirring for 2 h at 50 degrees -->adding MMA monomer --> polymerizing---> result: PMMA
Preparation of micron Si@C anodes for lithium ion battery by recycling the lamellar submicron silicon in the kerf slurry waste from photovoltaic industry[11][edit | edit source]
- kerf slurry waste (Si) --> down to sub micrometer size through ball milling
- reacting with glucose and form micron SiC --> Si in the core & glucose around Si
- storing Li ions inside si
- damping the Si expansion & electrical conductivity by carbon
- Battery assembly: 250 g of SiC & Super P & PAA (8:1:1) in 1 mL distilled water---> casting in 100 micrometer thickness---> dry in vacuum at 70 degrees for 10h--> cooled at room temp.
- CR2032 coin cell
- Battery components: 1) Celgard 2500: separator, 2) was LB-044 consisted of an organic solution of 1.0 M LiPF6 in ethylene carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC) (1:1:1 by volume) with 10.0% fluoroethylene carbonate (FEC) and 2.0% vinylene carbonate (VC): electrolyte, 3) metallic lithium: counter electrode
- acceptable Si size for LIB: 50-100 nm (reference 52)
- Considering each dimension separately -->the particle with nm size in one direction---> the volume expansion in that direction
- from FT-IR: Si-C bond
Equipment | ball mill | autoclave | ||||||||
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Material | 2.2 g of 500 nm Si particles | 4.5 g glucose | 0.9 g Ni nitrate hexahydrate (catalyst) | 50 mL distilled water | ||||||
Steps | ball milling the kerf slurry waste with 3-mm ball size | Mixing powders with water | heat the mixture in oil bath in autoclave in 190 degrees for 6 h | further carbonize the mixture at 700 degrees under N2 for 3h | adding graphene during preparation to increase the conductivity | |||||
TESTS | Zetasizer Nano ZS (for particle size) | SEM | FESEM | EDS | XRD | FT-IR | Raman spectra | XPS | galvanostatic charge/discharge (battery test system) | electrochemical impedance spectroscopy (electrochemical workstation) |
Results | specific discharge capacity is 3210.5 mAh/g for 0.1C | reversible capacity 1788.9 mAh/g after 200 cycles |
High-performance LiFePO4 and SiO@C/graphite interdigitated full lithium-ion battery fabricated via low temperature direct write 3D printing[12][edit | edit source]
(great source for analysis)
- Direct ink printing of SiO@C/ graphite comb-like structure.
- The solid content: 40%
- The weight ratio of SiO/graphite, CNT, and binder: 70:20:10.
- SEM images: the printed parts line width & thickness --> more than the aimed print --> material expansion after flowing out of the nozzle & large initial gap between nozzle tip and the bed at the beginning of the printing process.
3D printer info and variables | direct writing 3D printing | Comb-like design | -20 degrees printing temp | 418, 692, 806 micrometer thickness | 39.2, 60.9, and 84.3 mg/ cm2 mass loading | nozzle tip 260-610 micrometer | weight ratio (70:20:10 for SiO/graphite+ CNT+binder) | best solid content is 40% | extrusion speed 15 percent | scanning velocity 8 mm/s | layer thickness 0.2 mm | |
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Equipment | ultrasonic | |||||||||||
Material | LFP cathode | SiO@C anode | CNT (conductive) | styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) (binder) | 1,4 dioxane and de-ionized water (solvent) (high freezing temp) | Al and Cu current collector | Li-foil counter electrode | lithium hexafluorophosphate (LiPF6)-ethylene carbonate (EC), methyl ethyl carbonate and dimethyl carbonate plus a 2% solution offluoroethylene carbonate (FEC) (1.0 M LiPF6 EC: EMC. DEC ¼ 1:1:1 þ 2% FEC) (electrolyte) | ||||
Steps | CNT in solvent (ultrasonic for 2h) | Add CMC (stir magnetically for 12 h) | Add SiO@C/graphite powder (stir mechanically in vacuum for 4h) | Add SBR (stir mechanically for 4h in vacuum) | vacuum filtering | 3D print | freeze dry for 12 h | |||||
TESTS | coin like half cell for SiO@C/graphite | coin full cell for SiO@C/ Graphite and LFP | rheological properties | optical microscopy | SEM | EDS | porosimetery | Charge/ discharge | rate performance | cycling performance | cyclic voltametry | impedance spectroscopy |
Results | 17.9, 26.7 and 33.2 mAh/cm2 at 0.3C areal capacity (based on thickness) | porosity is 60% | The best result is from 418 thickness and 269 line width which has 276 mAh/g @ 3C specific capacity |
Ultrastable Silicon Anode by ThreeDimensional Nanoarchitecture Design[13][edit | edit source]
- Solving the issues of fracture, conductivity, and instability of SEI of Si anode.
- Slurry coating: LiFePO4 powder, carbon black and polyvinylidene fluoride (PVDF) in a weight ratio of 8:1:1
- prototype full cells: assembled by paring NG@Si-30@HSi anodes with LiFePO4 cathodes--> commercial viability of the hybrid Si anodes.
- Before assembling full cells--> stabilizing the N-G@Si-30@HSi anodes in the half cells for 20 cycles --> eliminate the irreversiblity.
Equipment | |||||||||
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Material | attaching Synthesis of N-doped Graphene@Si@Hybrid Silicate to Al rod with conductive silver epoxy (working electrode) | scattered Li metal on a tungstan rod as reference and counter electrode | Whatman glass fiber as the separator | LiPF6 dissolved in ethyl carbonate and diethyl carbonate (1:1 in volume) with 5 wt % fluoroethylene carbonate additive (electrolyte) | |||||
Steps | add N-doped graphene on Ni substrate using CVD | loading Si on graphene using RF magnetron | Synthesis of N-doped Graphene@Si@Hybrid Silicate by vapor deposition method | ||||||
TESTS | Phase | EDS | SEM | TEM | XPS | Raman | galvanostatic cycling of CR2032-type coin cells (Hokuto battery testing system) | electrochemical impedance measurement | R2032-type symmetric cells |
Results |
Drop‑on‑demand 3D‑printed silicon‑based anodes for lithium‑ion batteries[14][edit | edit source]
(just in case, ink preparation is provided)
- coating carbon on SiNi nanoparticles.
- the ratio of SiNi/sucrose/ CNT: 77.4/22.1/0.5 %wt
- the CNT: suspension of 0.2% CNT & 0.4% PVP in water
- LiPAA: dissolution of PAA in water --> heat to 60 for 3 days --> stir with lithium hydroxide (1:1 molar of carboxyl to hydroxide)
- CELL ASSEMBLY:
- drying printed anodes under vacuum at 50 degrees for 12 h and at 100 degrees for 2h
- assemble the CR2032 coin-cell type setup.
- anode detachement from the Cu when drying.
- NaPAA: water absorbance --> shrinkage when drying
3D printer info and variables | strips geometry and cast-like geometry | 600-800 micrometer distance between printed lines | ||||||||
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Equipment | pyrolyze furnace | mortar and pestle | polypropylene (Celgard 2400) as seperator | 15-mm lithium metal discs as counter electrode | 0.85 M lithium hexafluorophosphate in a mixture of ethylene carbonate, diethyl carbonate (1:1) with added vinylene carbonate (2%) (Solvionic), mixed with 15% fluoroethylene carbonate (SolvayFluor) as electrolyte | Cu current collector | ||||
Material | Si | NiNPs | CNT | sucrose | raphite as active material | LiPAA in water as binder | ||||
Steps | Mix Si and Ni (1:0.3) | dry | heat treat at 900 for 2 h | add CNT and sucrose in water | dry | pyrolyze at 1000 degrees for 1h | grind manually | add to ink slurry | add graphite+ LiPAA
(the final ratio is 80:10:10) |
|
TESTS | battery cycling | EIS | SEM | EDS | TGA | |||||
Results |
3D Printed Multilayer Graphite@SiO Structural Anode for High-Loading Lithium-Ion Battery (good good good)[15][edit | edit source]
preparing GS ink and Gt ink-based electrode--> Direct ink printing. (good for Victor's printer)
- The ratio of Gt and SiO: 4:1.
- active material: mixed with acetylene black and PVDF (7:2:1) in NMP.
- two nozzles to print Gt and GS layer after layer.
- The assembled full cell with 3D printed lithium nickel manganese oxide (LiNi0.5 Mn1.5O4, LNMO) cathode
Nano-silicon @ soft carbon embedded in graphene scaffold: High-performance 3D free-standing anode for lithium-ion batteries[16][edit | edit source]
(This introduces the surfactent for Si)
- making an anode with SiNP in soft carbon and graphene scafold.
- soft carbon: decrease volume expansion & prevents SEI formation
- Soft carbon: crystalline and amorphous regions for Li ion diffusion.
- The SiNP: evenly distributed in graphene --> eliminating the collision of SiNP--> electronic conductivity, Li ion diffusion, and high SiNP content.
- Mass ratio: SNPs/ graphene/SBL 6:3:1
- GSCS: SNPs/ graphene/SBL then heat treatment
- Si/G: similar to GSCS without heat treatment
- PDDA: as cationic polyelectrolyte--> large positive charge on the SNPs surface
- SBR: polymer containing H and C --> C without impurity.
Equipment | |||||||||||||
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Material | SiNP | Diethylene glycol diacrylate phthalate (PDDA) (it activates the Si particles) | Styrene-butadiene latex (SBL) | Graphene | |||||||||
Steps | 1 g SNP in 10 mL PDDA aquas solution and stir it for 4h, then wash it with DI water, then dry it in vacuum at 40 degrees for 24h | 0.3 g graphene and 0.7 g of the prepared SiNPin 100 mL DI water, stir for 4h at 40 degrees, filter and dry at 40 degrees in vecuum | 0.1 g of the previous into 4 g SBL, ultrasonic for 30 min, pour in glass mould, soft-bake at 40 degrees to make rubber | treat the mixture at 500 degrees in Ar gas for 4h | |||||||||
TESTS | SEM | TEM | XRD | Raman | XPS | potential analysis | FT-IR | TG | DSC | Digital multimeter (we use it when the materials are punched into 14.2 mm diameter electrode) | tensile test | galvanostatic discharge/charge with battery testing syste | EIS |
Results |
Flexible free-standing graphene-silicon composite film for lithium-ion batteries[17][edit | edit source]
- synthesizing graphene-Si for Li batteries --> in-situ chemical method with graphite oxide.
- previous works: highest battery performance --> 45% Si and 55% C.
- free standing composite film--> lower conductivity rather than metal substrate--> less Si in this work.
- the graphene in the composite:
- preventing Si particles from agglomeration
- elastic matrix to accommodate mechanical stress
- keep the structural integrity.
- voids to buffer the volume change --> the electrode is not pulverized (we still have expansion)
- graphene -->lowering the internal resistance for both e and ions (this makes the de alloying easier)--> easier ion transformation
Equipment | |||||||||
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Material | Si | GO | |||||||
Steps | 5 mg SiNP into 200 mL GO dispersion with 200 mg NaOH and 290 mg pyrenebutyric acid | 2h ultrasonication | reducing (graphite to graphene) with 1 mL hydrazine monohydrate at 80 degrees with stirring for 24h | cool to room temp | PVDF in 50:50 DI water to ethanol for 30 min | pssing the GO/Si from VDF filter in a filtration cell to produce free-standing Graphene-Si | washing with DI water | remove from PVDF after drying in vacuum at 60 overnight | heat treat at 500 for 10h in Ar to remove -H and -OH |
TESTS | FE-SEM | TEM | XRD | EDS | TGA | CR 2032 coin (Li foil counter and reference electrode, 1 MLiPF6 in a 50:50 (v/v) mixture ofethylene carbonate and dimethyl carbonate as electrolyte) | charge/discharge | raman | |
Results |
Waste glass microfiber filter-derived fabrication of fibrous yolk-shell structured silicon/carbon composite freestanding electrodes for lithium-ion battery anodes[18][edit | edit source]
(introduces a way to reduce the waste (SiO2) to Si)
- the waste glass fibers: amorphous with a wide range diameter ranging from nm to micrometers
- deep MgR: for extracting Si -->turns the waster to Mg2Si and MgO.
- the oxidation: Mg2Si to Si and MgO.
- HSl washing -->remove the MgO
- battery test:
- the samples: active materials (80%)
- ketjen black: conductive material (10%)
- sodium carboxymethyl cellulose (10%) in DIW.
- slip-casting the materials on the Cu foil and punching
- different electrodes with different time of carbonization: 30 min carbonization--> the optimum one.
Equipment | galvanostatic cycler | Swageloktype half cells | electrical oven | |||||||
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Material | waste glass | Magnesium powder | ketjen black | sodium carboxymethyl cellulose | copper foil | counter electrode: Li metal foil | seperator: GF (GF/F, Whatman) | 1.0 M LiPF6 electrolyte in ethylene carbonate/dimethyl carbonate (EC/DMC; 1:1 v/v, Sigma-Aldrich) with 10 vol% fluoro-ethylene carbonate (Soulbrain) additive | HCl | DI water |
Steps | mixing and annealing 0.16 g of glass with 0.32 g Mg powder
the anneal was for 10 h at 600 degrees in Ar |
we get Mg2Si after this step | heat treat the mixture for 5h at 600 degrees to change the structure to MgO and Si | immerse the mixture in HCl for 1h to remove the MgO | wash the precipitance wtith DI water | freeze the sample under -30 degrees and dry uder vacuum for 12 h | punch the material into 1 cm diameter disks | using acetone, the Si is coated with carbon through CVD | immerse the disks into HCl and same washing prodess | dry the samples in electrical oven at 90 degrees for 12 h |
TESTS | FE-SEM | XRF | XRD | TEM | elemental analysis | Brunauer-Emmett-Teller analysis | ||||
Results |
The preparation of SiC ceramic photosensitive slurry for rapid stereolithography**[19][edit | edit source]
(For choosing the polymer resin, photoinitiator and dispersant)
- SiC powder: high optical absorbance & refractive index --> reducing the penetration depth and curing thickness
- print SiC with less solid content--> still shrinkage & deformation after debonding
- acrylate monomer: high curing rate --> 40% of solid content--> printable layer thickness: 70 um --> npt good for big parts
- graded silica --> improve the curing thickness & rheological & settling performance
- using LSI method to fabricate SiC
- slurry: high solid content, low viscosity, low sedimentation rate and high curing thickness
- solving shrinkage problem after sintering: as high solid content as possible
- final SiC particle size: 30 um
- mixing: mechanically
- average particle size, volume fraction particles, spacing between particles, and the refractive index difference between the ceramic and the solvent ---> penetration depth --> curing thickness
- The bigger the particles, the less the absorbance, the more the curing thickness.
- The bigger the particles, the more the sedimentation and viscosity.
- The more the solid content, the less the curing thickness.
- The more the solid content, the less the sedimentation.
- The lower the viscosity of the resin, the higher the solid content we can add, the higher the curing thickness.
- for curing thickness more than 500 um in ceramics (low absorbance and refractive index): particles size less than 1 um
- SiC curing thickness--> less than SiO2
- polyethylene glycol ratio (7.5%): disperse the Si particles & decrease the viscosity & increase the solid content & increase the density & low the sedimentation
- coarse SiO2: improving the viscosity and the sedimentation performance
- SiO2: interlayer bonding in the deep layer.
- The finer the SiO2, the higher the viscosity, the smaller the curing thickness.
- The finer the SiO2, the less the sedimentation.
- BAPO: high initiating activity and wide absorption wavelength --> diffusing light to the deeper parts to cure the resin
- The ratio of photoinitiator (2%): if low--> high light intensity threshold, if high: curing the resin quickly and preventing the UV to penetrate the layers
- Oxygen: consuming the free radicals (negative effect)
- Exposure energy: Less exposure energy, more printing accuracy, smaller curing thickness.
- More laser power, larger the curing thickness (up to an amount, 147 mW/cm^2).
- The best curing thickness: 120-130 um & the printing accuracy: 70-100 um.
- Too high laser energy : thermal stress--> deformation
- The higher the speed, the less the received energy by the slurry, the smaller the curing thickness.
Stereolithography‐based additive manufacturing of gray‐colored SiC ceramic green body**[20][edit | edit source]
(Reference 30 for the proper viscosity, spectrometry)
- oxide ceramic colors: white and light
- SiC color: dark and gray --> impact on the light transferring behavior and the ability of curing
- UV light on the ceramic particles (the input light) --> the light energy absorbed by the ceramic particle--> the output light: small
- The absorbance value of the SiC: 0.417
- exposure time: 90 s --> increasing the exposure energy--->increased the curing thickness.
- The smaller the particle size, the worst the curing ability since they absorb more light
- the more the solid content the more the absorbance, the less the curing quality
Stereolithography 3D printing of SiC ceramic with potential for lightweight optical mirror[21][edit | edit source]
- fabrication of SiC using SLA
- ball milling with zirconia balls for 6 h.
- After printing: polymer burn-out (800), pre-sintering (1800), and precursor infiltration and pyrolysis (PIP)
- the result after PIP: separated silicon, no more layered structure --> making bridges through sintering --> grain boundaries --> denser structure--> still pores due to the burnt out polymer
- PCS--> precursor for PIP --> pore filling
- SiC to resin: 1:1
- total solid loading: 45%
- photoinitiator: 2wt% relative to resin
- dispersant: 5wt% relative to SiC
Materials | Printing setups | Tests |
---|---|---|
Micron-size SiC (average 15 um) | UV light wavelength: 405 nm light | Archimedes’ method: density |
Nano-size SiC (average 40 nm) | thickness: 50 um | three-point bending tests: flexural strength |
Al2O3 (sintering additive) | Exposure energy: 7500 uW/cm2 | SEM: microstructure |
Y2O3 (sintering additive) | Exposure time: 90 s/first layer | XRD: crystalline phase |
HDDA (monomer) | Exposure time: 15 s/other layers | |
TMPTA (monomer | ||
TPO (photoinitiator) | ||
KOS110 and 17000 (dispersant) | ||
Polycarbosilane (precursor) | ||
DiVinyl-Benzene (solvent) |
Dispersion and stability of SiC ceramic slurry for stereolithography[22][edit | edit source]
- DLP
- the effect of different parameters on the SiC slurry stability: 1) resin, 2) dispersant, 3) particle size, 4) solid loading, and 5) ball milling time
- mixing particles --> ball milling with zirconia (everything together including the dispersant)
- two different monomers (HDDA & TMPTA) with different ratio: effect of resin on the polymerization
- molecular weight of HDDA --> smaller than TMPTA --> the higher the HDDA the lower the viscosity
- viscosity for streolithography: 0-10 Pa.s
- cross-linking degree of HDDA: small --> the higher the HDDA the lower the curing thickness
- curing thickness: 5-10 um higher than the designed sliced thickness
- the higher the HDDA the higher the resin stability
- the effect of the dispersant (4-6%): low concentration--> many particles not modified--> adherence and agglomeration of the particles --> high viscosity
- high concentration: free dispersant molecules in the inter-particle framework --> high viscosity
- best dispersant: 5 % of KOS110 + 17000
- the effect of the particle size: Smaller particles--> high specific surface area & high specific surface energy -->dispersing easier than bigger particles
- small particles: negative effect on the high solid loading --> mix of particles preferable (smaller for dispersion and bigger for solid loading)
- small particles: negative effect on the viscosity --> low curing thickness--> best choice: 0.5 to 1% of nano particle size
- mix of particle size --> no sedimentation
- for particles: 2 forces: gravity & dispersion
- bigger particles: higher gravity
- smaller: almost equal gravity and dispersion force --> good dispersion
- solid loading (40%): the higher the solid loading the better the mechanical properties after sintering
- high solid loading: high viscosity and low curing thickness
Materials | Printing setups | Tests |
---|---|---|
Micron-size SiC (average 15 um) | UV light wavelength: 405 nm light | Rotational rheometer: rheological performance |
Nano-size SiC (average 40 nm) | thickness: 50 um | static sedimentation method: stability of the slurry |
HDDA (monomer) | Exposure energy: 7500 uW/cm2 | Digital micrometer: curing thickness |
TMPTA (monomer) | Exposure time: 30 s | Rotational rheometer: rheological performance |
TPO (photoinitiator, 2 wt% relative to the total resin mass) | ||
KOS110, 17000, 20000, 27000, and a KOS110 + 17000 dual (dispersant, ) | ||
Polycarbosilane (precursor) | ||
DiVinyl-Benzene (solvent) |
Fabrication of SiC ceramic architectures using stereolithography combined with precursor infiltration and pyrolysis[23][edit | edit source]
- polymer burnt out after printing (800)
- the viscosity for SLA: 5-10 Pa.s
- the higher the solid loading--> the lower the curing thickness
- the higher the solid loading--> the lower the density --> the less the flowability, the more the bubbles along the layer boundaries
- the more the solid load --> the less the amount of resin to connect the particles together--> the more the pores in the structure--> the less the strength
- after the pyrolysis: the higher the solid content the lower the shrinkage
Materials | Printing setups | Tests |
---|---|---|
SiC (30, 35, 40vol%) (average 1.1 um) | UV light wavelength: 405 nm light | Rotational rheometer: viscosity |
HDDA (monomer) and triethyleneglycol divinyl ether (DVE-3) (monomer) (1:1) | Slice layer thickness: 50 um | Archimedes’ method: desnity after polymer burnt out |
TPO (free radical photoinitiator, 1wt% based on the slurry weight) | Exposure energy: 7500 uW/cm2 | Digital micrometer: curing thickness |
(4-Methylphenyl)[4-(2methylpropyl)phenyl] iodonium hexafluorophosphate (cationic photoinitiator, 1wt% based on the slurry weight) | Exposure time: 90 s | TG-DTA: Binder burnout behavior |
KOS110 (dispersant, 5wt% based on the slurry weight) | XRD: crystalline phase | |
Three-point bending test: strength | ||
SEM: microstructure |
Stereolithography additive manufacturing and sintering approaches of SiC ceramics[24][edit | edit source]
- temperatures: polymer burnt out: 800, pre-sintering: 1800 in graphite furnace, curing: 60 degrees, pyrolysis 1200
- viscosity: 0.65
- shrinkage after the polymerization: 0.7%
Materials | Printing setups | Tests |
---|---|---|
Nano- and micron-sized SiC (40vol%) | UV light wavelength: 405 nm light | Archimedes’ method: desnity after polymer burnt out |
HDDA (monomer) and TMPTA (monomer) | Slice layer thickness: 25 um | Digital micrometer: linear shrinkage |
TPO (free radical photoinitiator, 1wt% based on the slurry weight) | Exposure energy: 7500 uW/cm2 | XRD: crystalline phase |
KOS110 and 17000 (dispersant, 5wt% based on the slurry weight) | Exposure time: 90 s (first) & 15 s (others) | Three-point bending test: strength |
SEM: microstructure |
Mechanochemical Synthesis of Fe−Si-Based Anode Materials for High-Energy Lithium Ion Full-Cells[25][edit | edit source]
- ball milling the Si powder with Fe powder
- WC balls
- drum volume: 80 mL & powder mass: 2.5 gr & rotational speed: 350 rpm
- Fe to Si ratio: 14:86 (here the weight ratio is 1:3), 20:80, 25:75, 33:67 atom %.
- heat treatment: 750 or 100 degrees for 10 h
- adding graphite (15%) & milling
- final mass ratio of active material, PAA binder and conductive agent: 85:10:5
- After milling more than 120 min: Fe to inactive Fe Si2
- more FeSi2 more stable cycling performance less reversible specific capacity, capacity retention, average lithiation and delithiation potential, or initial CE
- the smallest crystallite size while increasing the crystallite size --> the longest cycle life & reducing the cycle life
Tests |
---|
XRD: investigation the bulk structure.
Micrometrics by physisorption surface analyzer: to measure the specific surface area. BET Raman SEM EDX Tapped density analyzer Particle size analyzer: for particle size distribution TGA |
Properties of Fe–Si Alloy Anode for Lithium-Ion Battery Synthesized Using Mechanical Milling[26][edit | edit source]
- Si: Fe -->85:15
- ball to powder ratio--> 15:1
- speed: 650 rpm
- binder: PAA
- alpha FeSi2: metallic high temperature & beta FeSi2: semiconducting low-temperature
- after milling: Si surrounded by FeSi2
- when alpha FeSi2: high conductivity
- more ball milling --> beta FeSi2 --> less conductivity
- more milling time: SEI inside the particles
Silicon-Based Lithium-Ion Battery Systems: State-of-the-Art from Half and Full Cell Viewpoint[edit | edit source]
- SiOx --> less volume change but the side reactions --> formation of by-products & poor CE--> compensate by modifications.
- Electrolyte decomposition & SEI formation <-- plateau from 0.8 to 1.2 v
- reacting Si and Li+ --> 0.1-0.2 v
- Fracture of Si--> SEI breakdown --> consuming more Li+
- Solution1: Using polymer binder ---> but strong adhesion in polymer --> mechanical fatigue
- Solution 2: increasing the content of hydrogen bonds
- Solution 3: developing highly elastic polymer binders
- Solution 4: Prelithiation
- bulk silicon:
- higher ICE in micro size silicone but particle fracture and electrochemical polarization
- ball milling Si waste with SiC and Ni --> composite containing Si-SiC-Ni
- treating Si with ether and nitric acid and then co-sintering with graphite and sucrose --> SiC
- core-shell structure:
- solving silicon powders to the polymer (PVB) and then pyrolysis
- -------------
Research progress on silicon/carbon composite anode materials for lithium-ion battery[edit | edit source]
- SiC composite:
- core-shell
- yolk-shell
- porous structure
- embedding structure
- Core shell:
- carbon sources: sucrose, resin, acrylonitrile, polyvinyl alcohol (PVA), polyoxyethylene (PEO), polyvinyl chloride (PVC), polyethylene (PE), chlorinated polyethylene (CPE), pitch and polyvinylidene fluoride (PVDF) (the most optimum one)
- In SiO: li in the structure--> forming Li4SiO4 ---> mechanical support
- Yolk-shell:
- coating silicon wit SiO2 --> coat with another layer mesoporous (for resin diffusion) ---> converting the resin to C by heating
- acid washing --> solving O---> Si/void/ carbon
- more voids --> less structure degradation
- porous structure: providing path for the li ion penetration and volume change alleviation--> 3D printing
- getting p-Si/C or Si/p-C
- p-Si: magneseiothermic --> expensive
- SiOx /C:
- better cycling performance of SiO2 --> Si-O--> stronger bonds than Si-Si & producing lithium silicate and Li2O --> volume change alleviation --> carbon coating--> higher efficiency
- SiOx--> commercially used--> low ICE <-- irreversible electrochemical reaction between lithium ion and SiO2
- embedding type:
The synergistic effects of combining the high energy mechanical milling and wet milling on Si negative electrode materials for lithium ion battery[27][edit | edit source]
- combination of ball milling and wet milling.
- The silicon powder --> submicron and nano size.
- The process fractured the silicon particles
- The powders --> in amorphous and nanocrysralline phases.
- The wet milling --> enhance the SEI formation --> trigger the Si-O-CH2CH3 bonding on Si surface.
- The powder --> suppress the formation of the Li15Si14 during lithiation and delithiation <--- crystallin structure.
Si:C:Binder | 65:20:15 |
Si active material loading | 0.9 mg /cm2 |
coin-type | 2032 coin-type cells |
counter electrode | lithium foil |
Separator | Celgard 2300 |
Electrolyte | 1 M LiPF6 in a mixture of ethylene carbonate (EC, Ferro Co.), dimethyl carbonate (DMC, Ferro Co.) (1:1 by weight) and additive of 10 wt% fluorinated ethylene carbonate (FEC, Sigma-Aldrich Co.) |
discharge (lithiation)/charge (delithiation) | 0.02 and 1.5 V versus Liþ/Li |
Cyclic voltammetry (CV) | potential range of 0.005e2 V (vs. Liþ/Li) |
Cyclic voltammetry (CV) scan rate |
scan rate of 0.1 mV /s[edit | edit source] |
A novel approach to synthesize micrometer-sized porous silicon as a high performance anode for lithium-ion batteries[28][edit | edit source]
- microemulsion of cost-effective silica nanoparticles and magnesiothermic reduction
- Spherical micron-sized p-Si particles from this approach:
- Consist of highly aligned nano-sized silicon
- Exhibit tap density similar to bulk Si particles
- Improved electrochemical stability compared to nano-Si
- Features well-controlled void space and highly graphitic carbon coating on p-Si particles
- High tap density due to close packing structure (micrometer size silicon)
- High volumetric capacity of electrode (high tap density)
- Particle size range: 500 nm to 10 um, average: 5.28 um
- Wider particle size range results in higher tap density
- Nanometer pores inside structure (ability to buffer volume change)
- Silicon surface modified with carbon coating
- Carbon coating thickness: 5nm
- TGA: Determines carbon amount on silicon parts (17.3 wt%)
- Carbon coating is graphitic in nature
- Homogeneous distribution of carbon particles in silicon (improves electrochemical performance)
Benchmarking the Effect of Particle Size on Silicon Anode Materials for Lithium-Ion Batteries[29][edit | edit source]
- Crystal-to-amorphous phase transition during cycling (nano and micro size silicon)
- Different composition transition during de/lithiation (nano and micro size silicon)
- Thinner SEI in micro size
- Different composition of SEI (micro and nano size)
- Micro-size silicon powders prepared by ball milling
Effect of Size and Shape on Electrochemical Performance of Nano-Silicon-Based Lithium Battery[30][edit | edit source]
- Silicon nanoparticles vs. silicon nanowires comparison:
- Nanoparticles have higher initial specific capacity (3000-3500 mAh/g vs. 2500-300 for nanowires).
- Coulombic efficiency correlates linearly with silicon's specific area.
- Long-term cycling:
- Nanoparticles exhibit faster fade due to internal resistance.
- Nanowires show cycle stability.
- Critical diameter ranges:
- Nanoparticles and nanowires both in the range of 70-150 nm (not reliable due to different silicon sources, high size distribution, narrow average size range).
- Nanoparticles also in the range of 20-50 nm.
- Nanowires around 30 nm.
- Active material, conductive material, binder percentage: 50:25:25 (%).
- Carbon black contributes 100 Ah/g in specific capacity when measured independently.
Preparation of high solid loading and low viscosity ceramic slurries for photopolymerization-based 3D printing[31][edit | edit source]
- Smaller particle size → higher viscosity
- Higher solid volume fraction → higher viscosity
- 5% dispersant → lowest viscosity
- 2% photoinitiator → optimal curing process
- 40% solid loading → thickest curing depth
- Proper solid load particle size after ball milling: 0.35 um
- Ball milling done with zirconia balls
- Ball mill used as the mixing device
- Ball milling can trap air in the solvent, requiring consideration of defoamer agent or vacuum defoaming
- Lower viscosity is desirable, achieved with larger particles and lower solid content, but sedimentation increases
- Sedimentation is more important for print resolution
- Trade-off between sedimentation and viscosity
- Particle size most important factor in sedimentation; smaller size leads to less sedimentation
- Larger particles allow for higher solid load in the resin
- Longer exposure time results in thicker curing
- More photoinitiator (up to 2wt%) leads to thicker curing
- Excess photoinitiator can cause light absorption or scattering
- Increasing solid content reduces penetration depth and critical exposure
- Sliced layer thickness of printed sample should be smaller than penetration depth
- For 100 um sliced layer, maximum solid content is 40%, and particle size should be less than 3 um.
Materials | Cordierite powder (solid content) |
TMPTA: monomer | |
HDDA: monomer | |
propyl trimethoxysilane: surfactant | |
Disperbyk-111: dispersant | |
TPO: photoinitiator | |
Printing setups | critical exposure density: 0.73 and 2.73 mJ/cm2 |
Tests | DLS: particle size |
Rheometer: viscosity as a function of shear rate | |
Still settling tests: the stability of the slurries after preparation |
Controlling Surface Oxides in Si/C Nanocomposite Anodes for High-Performance Li-Ion Batteries[32][edit | edit source]
- Si oxide obtained by heating Si particles in the oven
- Time and temperature varied to control oxide layer thickness
- DMF and PAN used as carbon sources
- Core Si: crystalline structure, amorphous Si oxide surroundings
- FTIR results: Si-O-Si bonds, SiO4 bonds, O-Si-O bonds
- Carbon structure: floc-like, prevents Si agglomeration, forms conductive porous network
- Increasing oxide layer: SiOx to SiO2 transformation (negatively affects electrochemical, positively affects mechanical)
- Adjust oxide layer for different properties (e.g., 5 nm for high capacity, 8 nm for better cycling)
- 5 nm thickness: high capacity and cycle stability
- Thicker surface (>5 nm): better cycle stability, lower capacity due to limited lithiation
Silicon-Based Lithium-Ion Battery Systems: State-of-the-Art from Half and Full Cell Viewpoint[33][edit | edit source]
- SiOx:
- less volume change, side reactions, by-products, poor CE
- Electrolyte decomposition, SEI formation related to 0.8-1.2 V plateau
- Si and Li+ react at 0.1-0.2 V
- Fracture of Si results in SEI breakdown, consumes more Li+
- Polymer binder solution, but strong adhesion can lead to mechanical fatigue
- Increasing hydrogen bonds content as a solution
- Developing highly elastic polymer binders
- Crosslinking of Si/CNT
- Prelithiation for increased efficiency
- Bulk Si:
- Microsize Si higher ICE than nano-sized Si, but particle fracture and electrochemical polarization
- Reference 96: ball milling Si waste with SiC and Ni to create Si-SiC-Ni composite
- References 202, 203, 204: treating Si waste with ether and nitric acid, co-sintering with graphite and sucrose to obtain Si/C
- Core-Shell Structured Si Materials:
- Reference 205: core-shell Si/C created by dissolving Si powders into PVB polymer, then pyrolysis
- Reference 102: Si @ void @ C
- Reference 206: SiO2 covered by C, then Magnesiothermic treatment, possibly resulting in Si particles with double carbon coatings.
Research progress on silicon/carbon composite anode materials for lithium-ion battery[34][edit | edit source]
- Si-C Composite Categories:
- Core-shell:
- Carbon sources: sucrose, resin, acrylonitrile, PVA, PEO, PVC, PE, CPE, pitch, PVDF (optimal morphological performance).
- Doping Si with an element and then C improves results.
- Li+ penetration into SiO2 structure forms Li4SiO4 for mechanical support.
- Yolk-shell:
- Si coated with SiO2, then mesoporous layer for resin infiltration.
- Heating converts resin to C, acid washing removes SiO2, yielding Si/void/C.
- More void results in less structural degradation.
- Porous structure (for Li intercalation and volume alleviation):
- p-Si/C or Si/p-C structures.
- Making p-Si and p-C is complex; research ongoing.
- Larger porous particles needed for increased tap/packing density.
- SiOx/C type:
- SiOx structure has Si particles homogeneously distributed in SiO2 matrix.
- Si-O bonds are twice as strong as Si-Si bonds, leading to excellent cycle performance.
- Carbon coating improves efficiency.
- Low initial coulombic efficiency due to irreversible electrochemical reaction with SiO2; prelithiation helps.
- Embedding type:
- Silicone embedded in continuous carbon matrix as buffer.
- Graphite:
- Si particles intercalated between graphite flakes.
- Graphite stabilizes SEI layer, prevents Si particle agglomeration, and enhances electrical conductivity.
- Milling or CVD used to achieve structure.
- Poor adhesion requires polymer binder for interface bonding (e.g., Si/graphite/PAN, pelletizing, or ball milling with glucose and PVP).
- CNT/CNF:
- Si nanowires or nanotubes improve Li and electron transport but challenging electrode fabrication.
- Binders for Si:
- Traditional PVDF not suitable due to weak van der Waals interactions.
- New binders: carboxymethyl cellulose, polylactic acid-based, and alginate-based polymers form hydrogen bonds and/or covalent chemical bonds.
- More adhesion leads to greater Si involvement in reactions.
- 3D polymer chains (crosslinking) desired for stability.
- Abundant hydrogen bonds create self-healing properties for Si anode stabilization.
- Core-shell:
Si anode for next-generation lithium-ion battery[35][edit | edit source]
- Problems with Li-Si alloying and dealloying:
- Loss of electric contact with current collector and conductive materials.
- SEI formation causing irreversible capacity and poor cycling performance.
- Cracking and pulverization of Si.
- Particle size effect:
- Particles below 150 nm are desirable.
- Compositing effect:
- Provides mechanical strength.
- Enhances conductivity.
- Reduces contact area between electrolyte and active material.
- Composite matrixes include graphitic and amorphous carbon, metals, and oxides like MXene.
- Surface modification with organic functional groups helps form stable interfaces and maintain structural integrity.
- SiOx:
- Low volume change but large initial irreversible capacity in the first cycle due to Li2O and lithium silicate formation.
- Effective parameters on composite performance:
- Si and graphite size.
- Mass ratio of Si and graphite.
- Si distribution.
- Voids between electrodes.
- Preparation method.
- Structure design effect:
- Voids important for relieving deformable stress.
- Prevent electrical isolation formation, maintaining integrity.
- Different designs include solid Si core and hollow shell, porous shell, solid shell, porous Si core with solid shell, nanostructured Si embedded in porous and flaky matrix.
- Binder effect:
- Binders responsible for cohesion, should have stability, conductivity, self-healing, low cost, and eco-friendliness.
- Common binder, PVDF, lacks adequate integrity due to weak van der Waals forces.
- Alternatives: water-soluble binders, natural gum, hydrogel alginate, ion- and electron-conducting polymers, 3D network.
- Electrolyte additives:
- Characteristics include higher reductive potential, chemical compatibility, and film-forming properties.
- Impact morphology and composition of SEI.
- Examples: vinylene carbonate, fluoroethylene carbonate (for cycling stability and CE).
- Carbonate additives lead to crosslinked PEO and organic SEI components bonding to Si covalently.
- Conductive additives:
- Can be carbon black, CNT, CNW, Gr.
- Require excellent electrical conductivity, stability, strength, flexibility, and low cost.
- Structure considerations:
- 3D design of binder-free anode on current collector: promotes ion and electron transportation, strengthens Si-current collector contact, avoids detachment.
- Thin carbon layer: continuous electron path.
- Interconnection: fast ion/electron diffusion and increased electrode density.
- Porous SiNW: stress release and short ion diffusion path.
- 3D conductive framework within Si-based electrode: increases mass loading density, enhances mechanical property and electron migration, retards structural degradation.
- 3D current collector.
- Proper positive electrode choice to stabilize Si alloy in the negative electrode, e.g., LNMCO releases CO2.
- Advanced characterization techniques
- in-situ TEM to observe morphological changes (volume expansion) during lithiation and delithiation.
- Macropores in structure for stress reduction, thinner SEI layer, and better electrical contact.
- SEI layer:
- a passivation layer forming naturally on the electrode surface to avoid further reactions between electrode and electrolyte.
Using carbon black to facilitate fast charging in lithium-ion batteries[36][edit | edit source]
- Carbon black lattice space larger than graphite, enables fast charging.
- Work focuses on modifying CB content of graphite --> enhances energy density, and fast charging in Li-ion batteries.
Areal capacity of the anode | 3 mAh/cm^2 |
Anode Porosity | 33% |
Coin cell | coin cells (CR-2032) |
CD | voltage window of 0.01-2.0 V |
CD rate | under a 0.1C |
Anode loading | 9.8, 8.57, 8.92, 9.21, 9.81 mg/cm^2 |
Effect of Particle Size and Surface Treatment on Si/Graphene Nanocomposite Lithium-Ion Battery Anodes[37][edit | edit source]
- Four particle size ranges: 20-30 nm, 30-50 nm, 100 nm, 1-5 um.
- Silicon particles between graphene sheets.
- Bigger particles for more tap density.
- Higher tap density means higher loading weight.
- 20-30 nm highest specific surface area: higher surface area, less ion transportation path. More electrolyte consumption for SEI formation.
- Nanometer-sized silicon: round; micrometer-sized: flakes.
- Graphene: wrinkle flake.
- Composites show uniform distribution of Si, C, O.
- Micrometer size: highest crystallinity.
Si:C:binder | 70:15:15 |
coin
cell |
half- CR2032 coin cells |
counter electrode | Lithium foil |
electrolyte | 1 M LiPF6 dissolved in a mixed solution of diethyl carbonate (DEC) and ethyl carbonate (EC) at 1:1 vol ratio with 2 wt% fluoroethylene carbonate (FEC, 99%, Sigma-Aldrich) as additive |
CD voltage | between 0.001 and 1.5 V |
CD current rates | different current rates calculated based on the theoretical capacity of lithiated Li15Si4 at 3,579 mAh/g |
Si/SiC/C in-situ composite microspindles as anode materials for lithium-ion batteries[edit | edit source]
- Si/SiC/C in-situ composite microspindle fabrication process
- Utilization of Zn2SiO4/C nanowire bundles from hydrothermal synthesis
- In-situ generation and uniform distribution of SiC and C components
- Strengthening effect of SiC on microspindle structure
- High conductivity and buffering function of amorphous carbon
- Application as anode materials in lithium-ion batteries
- Reversible charge capacity of 1510 mAh g-1
- Initial coulombic efficiency of 78.7%
- Capacity retention of 89.9% after 200 cycles at 100 mA g-1
- Superior rate capability
- Enhanced electrochemical performance compared to pure Si microspindles
- Efficiency of composition and structural design of Si/SiC/C composite microspindles
- ↑ Petousis, M., Vidakis, N., Mountakis, N., Grammatikos, S., Papadakis, V., David, C.N., Moutsopoulou, A., Das, S.C., 2022. Silicon Carbide Nanoparticles as a Mechanical Boosting Agent in Material Extrusion 3D-Printed Polycarbonate. Polymers (Basel) 14, 3492. https://doi.org/10.3390/polym14173492
- ↑ Katsuyama Y, Kudo A, Kobayashi H, Han J, Chen M, Honma I, et al. A 3D‐Printed, Freestanding Carbon Lattice for Sodium Ion Batteries. Small 2022;18:2202277. https://doi.org/10.1002/smll.202202277
- ↑ Beydaghi H, Abouali S, Thorat SB, Del Rio Castillo AE, Bellani S, Lauciello S, et al. 3D printed silicon-few layer graphene anode for advanced Li-ion batteries. RSC Adv 2021;11:35051–60. https://doi.org/10.1039/D1RA06643A.
- ↑ Ye X, Wang C, Wang L, Lu B, Gao F, Shao D. DLP printing of a flexible micropattern Si/PEDOT:PSS/PEG electrode for lithium-ion batteries. Chem Commun 2022;58:7642–5. https://doi.org/10.1039/D2CC01626E.
- ↑ Zhao, K. & Cui, B. (2020) Synthesis of SiC Resin for 3D Printing of SiC Ceramics by Digital Light Processing. Poster presentation, UCARE Research Fair, Spring 2020, University of Nebraska-Lincoln
- ↑ [1] Guo Z, An L, Khuje S, Chivate A, Li J, Wu Y, et al. 3D-printed electrically conductive silicon carbide. Additive Manufacturing 2022;59:103109. https://doi.org/10.1016/j.addma.2022.103109.
- ↑ Li S, Zhang Y, Zhao T, Han W, Duan W, Wang L, et al. Additive manufacturing of SiBCN/Si 3 N 4 w composites from preceramic polymers by digital light processing. RSC Adv 2020;10:5681–9. https://doi.org/10.1039/C9RA09598E.
- ↑ Liu C, Qian B, Ni R, Liu X, Qiu J. 3D printing of multicolor luminescent glass. RSC Adv 2018;8:31564–7. https://doi.org/10.1039/C8RA06706F.
- ↑ Dizon JRC, Chen Q, Valino AD, Advincula RC. Thermo-mechanical and swelling properties of three-dimensional-printed poly (ethylene glycol) diacrylate/silica nanocomposites. MRS Communications 2019;9:209–17. https://doi.org/10.1557/mrc.2018.188.
- ↑ Canché-Escamilla G, Duarte-Aranda S, Toledano M. Synthesis and characterization of hybrid silica/PMMA nanoparticles and their use as filler in dental composites. Materials Science and Engineering: C 2014;42:161–7. https://doi.org/10.1016/j.msec.2014.05.016.
- ↑ Fan Z, Zheng S, He S, Ye Y, Liang J, Shi A, et al. Preparation of micron Si@C anodes for lithium ion battery by recycling the lamellar submicron silicon in the kerf slurry waste from photovoltaic industry. Diamond and Related Materials 2020;107:107898. https://doi.org/10.1016/j.diamond.2020.107898.
- ↑ Liu C, Zhao N, Xu K, Li Y, Mwizerwa JP, Shen J, et al. High-performance LiFePO4 and SiO@C/graphite interdigitated full lithium-ion battery fabricated via low temperature direct write 3D printing. Materials Today Energy 2022;29:101098. https://doi.org/10.1016/j.mtener.2022.101098.
- ↑ Huang G, Han J, Lu Z, Wei D, Kashani H, Watanabe K, et al. Ultrastable Silicon Anode by Three-Dimensional Nanoarchitecture Design. ACS Nano 2020;14:4374–82. https://doi.org/10.1021/acsnano.9b09928.
- ↑ Ben-Barak I, Schneier D, Kamir Y, Goor M, Golodnitsky D, Peled E. Drop-on-demand 3D-printed silicon-based anodes for lithium-ion batteries. J Solid State Electrochem 2022;26:183–93. https://doi.org/10.1007/s10008-021-05056-z.
- ↑ He W, Chen C, Jiang J, Chen Z, Liao H, Dou H, et al. 3D Printed Multilayer Graphite@SiO Structural Anode for High‐Loading Lithium‐Ion Battery. Batteries & Supercaps 2022;5. https://doi.org/10.1002/batt.202100258.
- ↑ Wang F, Hu Z, Mao L, Mao J. Nano-silicon @ soft carbon embedded in graphene scaffold: High-performance 3D free-standing anode for lithium-ion batteries. Journal of Power Sources 2020;450:227692. https://doi.org/10.1016/j.jpowsour.2019.227692.
- ↑ Wang J-Z, Zhong C, Chou S-L, Liu H-K. Flexible free-standing graphene-silicon composite film for lithium-ion batteries. Electrochemistry Communications 2010;12:1467–70. https://doi.org/10.1016/j.elecom.2010.08.008.
- ↑ W. Kang, J.-C. Kim, D.-W. Kim, Waste glass microfiber filter-derived fabrication of fibrous yolk-shell structured silicon/carbon composite freestanding electrodes for lithium-ion battery anodes, Journal of Power Sources. 468 (2020) 228407. https://doi.org/10.1016/j.jpowsour.2020.228407.
- ↑ J. Tang, X. Guo, H. Chang, K. Hu, Z. Shen, W. Wang, M. Liu, Y. Wei, Z. Huang, Y. Yang, The preparation of SiC ceramic photosensitive slurry for rapid stereolithography, Journal of the European Ceramic Society. 41 (2021) 7516–7524. https://doi.org/10.1016/j.jeurceramsoc.2021.08.029.
- ↑ G. Ding, R. He, K. Zhang, C. Xie, M. Wang, Y. Yang, D. Fang, Stereolithography‐based additive manufacturing of gray‐colored SiC ceramic green body, J Am Ceram Soc. 102 (2019) 7198–7209. https://doi.org/10.1111/jace.16648.
- ↑ G. Ding, R. He, K. Zhang, N. Zhou, H. Xu, Stereolithography 3D printing of SiC ceramic with potential for lightweight optical mirror, Ceramics International. 46 (2020) 18785–18790. https://doi.org/10.1016/j.ceramint.2020.04.196.
- ↑ [G. Ding, R. He, K. Zhang, M. Xia, C. Feng, D. Fang, Dispersion and stability of SiC ceramic slurry for stereolithography, Ceramics International. 46 (2020) 4720–4729. https://doi.org/10.1016/j.ceramint.2019.10.203.
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