light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries

Recently, efforts have been made to convert and store solar energy in one device. Herein, dye-
Synthetic solar cell technology and lithium-
Study of ion materials of light
Auxiliary battery charging.
Especially the direct photos we reported.
Oxidation of lithium iron phosphate nano-crystals in dye as mixed light
In two cathode
Electrode system, with lithium metal as the anode, adding lithium hexfluoride phosphate to lithium carbonate
Basic electrolyte;
Configuration corresponding to lithium ion battery charging. Dye-
The sensitivity increases the generation of electron-hole pairs, which help the lithium ion to disintegrate at the cathode, and the electron is reduced by oxygen to form a solid electrolyte interface at the anode.
Lithium iron phosphate effectively acts as a reversible oxidation reducing agent for dye regeneration.
Our findings offer the possibility to advance the principles of photo design
Rechargeable lithium ion battery. Lithium iodine (beads, ≥99%)
Lithium hydroxide, iron (II)
Chlorine without water (≥98%)
Seven water iron ore (≥99. 0%)
Lithium hydroxide water (≥98. 0%)
Phosphate (
85% w/w in water, ≥ 99.
9% base of trace metals)
Diammonium phosphate (≥98%)
Sodium hydroxide (solution 28. 0–30. 0% NH basis)
Vitamin C (≥99. 0%), oleylamine (>70%), 1-octadecene (>90%)
Ethanol and acetone, Di-
Ammonium tetrylbis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)ruthenium(II)dye (N719 dye, 95%)
, Thyl aldehyde (
THF without water, ≥ 9%)
, Tetramine ether (TEGDME, ≥99. 0%), -
1) methyl pyriconeNMP,>97%)
Ethylene carbonate (VC)(≥97%)and bis(
Trifluoride methane)
Lithium (LiTFSI)
Buy salt from Sigma Aldrich and carbon nanotubes from CNano Ltd.
Poly partial two (PVDF)
Purchased from Wu Yu 7305 (Japan).
These chemicals are used without further purification.
FTO was purchased from Cell Diagnostics.
Lithium metal is purchased from the lithium battery of the FMC.
EC/lipm LiPF, December 1 (3/7 +2%VC)
DME provides 1 m LiTFSI in DME/DOL and EC/December solutions.
LFP was synthesized by colloidal route.
In the typical colloidal synthesis test, 2. 25u2009g (16. 8u2009mmol)
Lithium iodine (LiI), 1. 65u2009g (12. 5u2009mmol)
Diammonium phosphate, 1. 575u2009g (12. 5u2009mmol)iron(II)
Chlorine, ml (0. 38u2009mmol)
Oleylamine and 25 ml 1-
Octadane mixed in 500 three-
Neck bottle attached to standard Schlenk line.
The solution maintains a vacuum of 1 h at 120 °c and then is heated to 250 °c for at least 3 h at N.
Then clean the suspended matter by repeatedly adding acetone and ethanol and then centrifuge at 8,000 u2009 r. p. m.
LFS nanoparticles are etched through LiPF treatment to remove the residual oleylamine ligand.
Colloidal LFP nanoparticles (400u2009mg)
Disperse in methane of 10 ml and dissolve 500 mg LiPF in water of 10 ml.
Mix the two solutions and shake the final 20 ml mixture violently.
After a few minutes, LFP nano-platelets are transferred to the aqueous phase and then collected and centrifuge at 8,000 u2009 r. p. m.
Super pure water (40u2009ml)(
Resistivity of 18 Ω m Ω cm)
Add to the powder to remove the excess LiPF from nc.
Then re-disperse nc in 5 ml ultra pure water.
The last step was repeated three times. A total of 5.
The etching LFP of 5g was prepared by this method.
In the standard thermal synthesis (
See previous publications for more details)33. 6u2009g (0. 12u2009mol)
FeSO 7HO, 1541u2009g (0. 36u2009mol)of LiOH HO, 13. 83u2009g (0. 12u2009mol)of HPO, 0.
Vitamin C of 5g (CHO)
Mix in the glass lining with 300 de-ionic water.
The final molar ratio between Li: Fe: PO: CHO is 3: 1: 0. 008.
The PH is controlled at 7. 8 by drop-by-
Drip addition of sodium hydroxide NHOH.
Synthesis in a stirring autoclave (OM-JAPAN).
Samples were collected at 80 °c after 5 µh.
Ball mill hot water LFP was obtained by ball mill SPEX 30 min.
In Quantachrome equipment, the specific surface area was measured by physical adsorption of nitrogen at 77 k, the autosorb iQ model.
The specific surface area is used morepoint BET (
Bruna-emit-teller)
In the model, the equal spacing points from 0 to 11 are considered in/range. 05 to 0. 35.
Sample before measurement (
50-200 mg in powder form)
Under vacuum, 1 u2009 h was Degas at 30 °c to eliminate the weakly adsorbed species. A total of 5.
LFP a nc of 5 u2009 g is dispersed in 57.
5 ml de-ionic water is set for 24 h under intense stirring, and then 0.
Add 4 ml of Triton X100 to the solution and stir for at least 48 hours.
Pause to be stirred violently for 48 hours before coating.
The film was prepared by using an RDC-immersion coating15 dip-
From Bungard coating machine.
These films are obtained after three soaking steps, with an interval of 20 µs between each step.
Between the two immersion, the film was pulled out at the rate of 5 cmmin min, dried for 4 min, and then soaked again.
The film is then annealing under nitrogen at 400 °c and cooled at room temperature in VBF-1200X oven (MTI company).
Prior to the annealing step, the oven was vacuum cleaned three times, cleaned under N flow for 1 u2009 h, and the substrate was placed in a graphite crucible to avoid LFP oxidation during annealing.
The film thickness is 2. 0 (±0. 2)μm ().
The density of LFP film is 1.
43 mgcm corresponding to 59% holes.
The electrode was prepared from a dipped/LFP film soaked in a 10 m ethanol solution containing Ru-
Dyeing N719 24 hours.
Then Vacuum dry the sample at 50 °c for 24 hours. A total of 5. 5u2009g of LFP, 0.
Carbon nanotubes of 30g, 0.
005 N719 dye and 0 of RWG.
The SPEX mixer, which adjusted the viscosity of the slurry with NMP solvent, mixed 30g of polyammonium diammonium 7305.
The final ratio of LFP: cnt: Poly Dione is 90: 5.
The amount of dye N719 is fixed to 5 mg for 5.
5g of LFP, added directly to the slurry when mixing with SPEX.
The viscosity of the slurry is adjusted by using methyl Pyron.
In PET/Sn: InO (PET/ITO)and laminated.
Cnt and 0 of 5g.
5g poly Dione with NMP to adjust viscosity.
The doctor\'s blade deposits the slurry on the ITO film.
Cnt N719 samples were prepared by adding 0 to the mixture.
005 dye for g N719.
Three in a dry room-
Electrode batteries using lithium metal as a reference electrode and CE, as well as our LFP on FTO/glass.
Electrolyte is 1 lipm LiPF in EC/December (3/7)+2% VC.
Record OCV data using a VMP3 potentiometer from Biologic.
OCV and constant current charge/discharge measurements are performed in light and dark.
About the experiment in Ar atmosphere, three-
Preparation of electrode batteries in Ar-
Fill the glove box and seal it with glue.
OCV measurement in a dry room.
Gex_analysis of the X of the PANalytical Sky
It is equipped with 1 x-ray diffraction.
8kw kw copper K ceramic X-
A tube that works under 45 kV and 40 kV.
The diffraction pattern was collected at room temperature, and the diffraction angle was 1.
The 2 angle range of 3 ° and 15-85 °, the step size is 0. 04°.
Suppression of Cu K radiation and X-by flat pyrolysis graphite Monometer-
Ray Fluorescence
The X-ray diffraction pattern shown is recorded in the Royal Intelligent Laboratory of Japan X-
X-ray diffraction equipped with 9kw kw Cu K rotating anode (
At 40 kV and 150 mAh)
And D/teX Super 1D detector set in X-
Light restore mode.
The diffraction pattern is collected at room temperature in a Prague-Brentano geometry with an angle range of 2 = 15-85 ° and a step size of 0. 025°.
The HRTEM image was obtained on jeol jem.
2200FS microscope at 200kv. A 20u2009eV slit (Ω filter)
Used to filter elastic scattering electrons to increase image contrast.
In spectral mode, EELS are obtained using a filter and the aperture and convergence angle are selected to provide the same sample acquisition conditions.
The spectrum is subtracted by the background and normalized after
The edge region of the Fe L spectrum to explain the thickness difference between samples.
The spectrum is eventually aligned on the energy of O-K (532u2009eV)and Fe-L (708u2009eV)edges.
The HRSEM observation shown in is the use of jeol jsm-
7500FA scanning electron microscope with cold field launch gun (
Single crystal tungsten emitter, final resolution of 1 kbps nm)
And operate at a voltage of 15 kV. A dual-beam high-
Resolution microscope from TESCAN (Czech Republic)
Also used for observation ()
Local chemical analysis using windowless energy dispersion spectrometer and extremely low electronic noise from Oxford Instruments (
See EDS analysis below).
XPS was performed on the Kratos axis ultra-DLD spectrometer using a monochrome Al K source (15u2009kV, 20u2009mA).
Wide Scanning was obtained under the energy transfer of ev\'s Analyzer. High-
A resolution narrow scan is performed with a constant of 10ev ev via energy and a step of 0. 1u2009eV.
Photoelectric was detected in one shot
Deviation from angle φ = 0 ° relative to surface normal.
For data collection, the pressure in the analysis chamber is kept below 7 × 10 tortorr.
The data is converted to VAMAS format and processed using version 2 of Casa XPS Software. 3. 16.
Bound energy (BE)
Scale is referenced internally as the c1 peak (BE for C–C=284. 8u2009eV).
On the Bruker Avance III spectrometer, H and f nmr spectra were recorded at 300 and 282 mhz, respectively.
The following abbreviations are used for multiple distributions: \"s\" of single states, \"d\" of double states, \"t\" of triple states, multiple \"m\" and generalized \"br\"
Methanol removed from scale (CDCN)
As a reference solvent (
Dilution factor = 5).
In h nmr, the spectrum is referenced to the solvent peak while Li-
PF is set to-76. 9u2009p. p. m.
As reported by Wilken, in f nmr. .
We tested five different electrolyte: 1 lipm LiPF + 2% VC in EC/December, 1 m LiPF in THF, 1 lipm LiPF in TEGDME, EC/2% VC and 1 m LiTFSI in 1 litm LiTFSI + DME/DOL in December.
2% VC and LiTFSI in LiPF + DME/DOL from EC/December are commercial products (See \"materials \"). LiTFSI (1u2009M)
In EC/December + 2% VC, 1 lipm LiPF in THF, 1 lipm LiPF in TEGDME (ref. )
It\'s not a commercial product, then it\'s prepared separately.
LiPF dissolved in THF and TEGDME;
No LiPF is written in DME/Dole due to DMEand DME/DOL)
Polymerization by LiPF reaction.
Raman measurements were carried out on the LabRaman Aramis spectrometer (
Jobbin Ivin horriba).
Laser with a wavelength of 532.
1 nm and Energy 1.
Focus on 3 mW with the goal of × 50.
The measurements were made between 100 and 1900 and the data collection time was 2 min.
EDS analysis using the newly developed very low energy EDS of Oxford Instruments (UK).
The detector uses very low noise and optimized electronics while removing any window to reduce the absorption of very low energy X-
Light in front of the detector crystal.
This detector is unique to hydropower.
Quebec and it are a joint result.
Cooperation between Oxford Instruments (UK)and H. Q (Canada).
The sun simulator was purchased from Sciencetech Inc. , model :(SLB-300B)
Small solar simulator class ABA with air quality am1.
5G filter as standard test condition.
In our support information, it is obtained by measuring the light source in our lab using a monochrome and thermoelectric detector.
Calibration with reference batteries (
Single crystal silicon solar cell photoelectric detector with size of 1 cm × 1 cm)
Purchase and calibrate from PV Measurements, Inc. , Model: RC1-G5.
When the reference cell is short
The output circuit current is equal to the short circuit value of its calibration.
Circuit current, which indicates that the irradiance reaching the reference unit is equal to the irradiance (one-sun)
This occurs during calibration.
When the reference cell is short
The output circuit current is equal to the short circuit value of its calibration.
Circuit current, which indicates that the illumination on the reference unit is equivalent to the standard one sun illumination after calibration (100u2009mWu2009cm).
In this way, we have identified
The sun works at a distance and then takes our picture-battery set-
Prepare for measurement.
Upon request, the corresponding authors provided data supporting the results of this study.