U.S. patent application number 13/534277 was filed with the patent office on 2013-06-27 for photoelectrode and method for preparing the same.
This patent application is currently assigned to National Cheng Kung University. The applicant listed for this patent is Chun-Ren KE, Jyh-Ming TING. Invention is credited to Chun-Ren KE, Jyh-Ming TING.
Application Number | 20130160837 13/534277 |
Document ID | / |
Family ID | 48653370 |
Filed Date | 2013-06-27 |
United States Patent
Application |
20130160837 |
Kind Code |
A1 |
TING; Jyh-Ming ; et
al. |
June 27, 2013 |
Photoelectrode and Method for Preparing the Same
Abstract
The present invention relates to an photoelectrode and the
preparation method thereof, wherein said photoelectrode comprises a
substrate and a titania layer composed of a mesoporous titania bead
having a diameter of 200-1000 nm, specific surface area of 50-100
m.sup.2/g, porosity of 40-60%, pore radius of 5-20 nm, pore volume
of 0.20-0.30 cm.sup.3/g, and the titania comprised in the bead is
anatase titania.
Inventors: |
TING; Jyh-Ming; (Tainan
City, TW) ; KE; Chun-Ren; (Tainan City, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
TING; Jyh-Ming
KE; Chun-Ren |
Tainan City
Tainan City |
|
TW
TW |
|
|
Assignee: |
National Cheng Kung
University
Tainan City
TW
|
Family ID: |
48653370 |
Appl. No.: |
13/534277 |
Filed: |
June 27, 2012 |
Current U.S.
Class: |
136/256 ; 438/98;
977/948 |
Current CPC
Class: |
C01P 2004/64 20130101;
C01G 23/047 20130101; C01P 2006/14 20130101; B82Y 20/00 20130101;
C01P 2004/03 20130101; B82Y 40/00 20130101; C01P 2006/40 20130101;
C01G 23/053 20130101; C01P 2002/72 20130101; Y02P 70/50 20151101;
C01P 2004/62 20130101; H01L 51/0021 20130101; C01P 2004/04
20130101; H01G 9/2059 20130101; C01P 2006/16 20130101; Y02E 10/549
20130101; Y02E 10/542 20130101; H01G 9/2031 20130101; B82Y 30/00
20130101 |
Class at
Publication: |
136/256 ; 438/98;
977/948 |
International
Class: |
H01L 31/0224 20060101
H01L031/0224; H01L 31/18 20060101 H01L031/18 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 21, 2011 |
TW |
100147646 |
Claims
1. A photoelectrode, comprising: (1) a substrate; and (2) a titania
layer composed of a mesoporous titania bead having a diameter of
200-1000 nm, specific surface area of 50-100 m.sup.2/g, porosity of
40-60%, pore radius of 5-20 nm, pore volume of 0.20-0.30
cm.sup.3/g, and the titania comprised in the bead is anatase
titania.
2. The photoelectrode according to claim 1, wherein said substrate
is a metal substrate, or a transparent non-conductive substrate
covered by a transparent conductive film.
3. The photoelectrode according to claim 1, wherein said titania
layer has a thickness of 5-10 .mu.m.
4. The photoelectrode according to claim 1, wherein said mesoporous
titania bead is prepared by the following steps: (1) adding a
steric agent and a titanium-containing precursor into ethanol to
proceed sol-gel reaction and give a sol-gel product, wherein the
molar ratio of said steric agent:said titanium-containing
precursor:ethanol is 0.1-1:1:200-300; and (2) heating said sol-gel
product in water at 120-200.degree. C. for 1-24 hours to obtain the
mesoporous titania bead.
5. The photoelectrode according to claim 4, wherein said steric
agent is a tertiary amine.
6. The photoelectrode according to claim 5, wherein said tertiary
amine is selected from hexamine, trimethylamine, quinoline,
isoquinoline or methyldiethylamine
(CH.sub.3N(CH.sub.2CH.sub.3)).
7. The photoelectrode according to claim 4, wherein said
titanium-containing precursor is selected from titanium
tetraisopropoxide, titanium tetrachloride, titanium trichloride,
ethyl orthotitanate or Ti(OC.sub.4H.sub.8).sub.4.
8. The photoelectrode according to claim 4, further comprising
adding a salt into said ethanol in step (1) to adjust ionic
strength to 1.times.10.sup.31 4-32.times.10.sup.-4.
9. The photoelectrode according to claim 8, wherein said salt is
selected from KCl, LiCl, NaCl, KCl, LiF, NaF, KF, LiBr, NaBr, KBr,
LiI, NaI, KI, CsCl, CsI, CsBr, KNO.sub.3.
10. The photoelectrode according to claim 1, wherein said titania
layer increases scattering efficiency and used as a scattering
layer.
11. The photoelectrode according to claim 1, further comprising a
titania nanoparticle layer between said substrate and said titania
layer.
12. The photoelectrode according to claim 11, wherein said titania
nanoparticle layer is composed of a titania nanoparticle, not
composed of said mesoporous titania bead.
13. The photoelectrode according to claim 12, wherein said titania
nanoparticle of the titania nanoparticle layer is P25, ST-01,
ST-21, ST-31, TTO-55S or ST-30L.
14. The photoelectrode according to claim 1, which is used for
manufacturing a cell.
15. A method for preparing the photoelectrode according to claim 1,
comprising: (4) providing a substrate; (5) coating a mesoporous
titania bead on said substrate to obtain a coated layer, in which
said bead has a diameter of 200-1000 nm, specific surface area of
50-100 m.sup.2/g, porosity of 40-60%, pore radius of 5-20 nm, pore
volume of 0.20-0.30 cm.sup.3/g, and the titania comprised in the
bead is anatase titania; and (6) pressing the coated layer from
step (2) under room temperature to obtain said titania layer.
16. The method according to claim 15, wherein said substrate is a
metal substrate, or a transparent non-conductive substrate covered
by a transparent conductive film.
17. The method according to claim 15, further comprising the
following step between step (1) and step (2): coating a titania
nanoparticle on said substrate to obtain a titania nanoparticle
layer, and said titania nanoparticle is not said mesoporous titania
bead.
18. The method according to claim 15, which is applied to cell
manufacture.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a photoelectrode and method
for preparing the same.
[0003] 2. Description of the Related Art
[0004] After industrial revolution, fossil fuel consumptions grew
dramatically accompanying with the development of science, and
resulted in fossil fuel exhaustion and environmental damages. For
sustainable survival, the development of renewable and alternative
energy was the ultimate goal of the world. In all alternative
energies, solar energy caught people's attention because it was
abundant and clean, and many companies had invested in the
associated research and development.
[0005] Solar cell, also called photovoltaic cell, was a device for
converting light energy into electrical energy. However, lots of
energy was consumed during the manufacture of solar cells, so it
was still a challenge for solar cells to reach grid parity. At
present, most commercial solar cells were silicon solar cells, in
which monocrystalline silicon solar cells and multicrystalline
silicon solar cells had a cell efficiency of 18% and 17%,
respectively. But the cost of silicon solar cells was high because
pure crystalline silicon materials were widely used in
semiconductor industry. Materials generally used for non-silicon
thin-film solar cells were cadmium telluride (CdTe) or copper
indium gallium diselenide (CIGS, CuInGaSe), in which the former
material was mainly used by First Solar for manufacturing solar
cells with the lowest price per watt in all commercial solar cells,
but cadmium contamination was a concerned issue; and the latter
material could be used for manufacturing stable solar cells with
high efficiency and long life span, but the complicated element
composition caused low yield rate.
[0006] A solar cell promising for dramatically reducing electricity
cost was dye-sensitized solar cell (DSC), which was published on
Nature in 1991 (B. Oregan and M. Gratzel, "A Low-Cost,
High-Efficiency Solar-Cell Based On Dye-Sensitized Colloidal
TiO.sub.2 Films," Nature, 353 (6346), 737-740, 1991). DSC had
advantages that it cost less and could be applied to flexible
applications. Comparing with silicon solar cells, it was less
influenced by incident angle and increased temperature, so the DSC
was very competitive and potential to lead the trend of the next
generation solar cells. There had been many commercial DSCs in the
market, for example, Sharp had manufactured a DSC having a high
cell efficiency of 10.4%. Generally, DSC had a shorter life span
and lower cell efficiency; however, if these disadvantages were
overcome, it would be the most widely used solar cell in the
future.
[0007] In DSCs, the photoelectrode was important for loading dye
molecules and transferring electrons, and it was the key to decide
cell efficiency. The main material for producing the photoelectrode
was titania nanoparticles. Titania (TiO.sub.2) was a stable,
non-toxic material with high refractive index (n=2.4-2.5), and
widely used in our daily life, such as in white pigment, tooth
paste, cosmetics or food. The naturally occurring titania had three
main crystal phases: rutile, anatase and brookite, in which the
rutile titania was the most stable crystal phase in view of
thermodynamics; but the anatase titania was suitable for cell
applications because it had a greater energy band gap and a higher
conduction band, so the anatase titania could reach a greater
quasi-Fermi energy level and open circuit voltage under the same
electron concentration, thereby achieving a better cell
efficiency.
[0008] Regarding with the morphology of titania, the titania
nanoparticles (NPs) was widely applied to DSCs because it had a
high specific surface area which was able to absorb a large amount
of dye. However, NPs did not have an oriented structure, and the
electrons immigrated in random directions, so the electron
collection efficiency was limited. In addition, the particle size
of NPs was too small to produce effective visible light scattering
and good light harvesting. Therefore, many strategies had been
taken to solve this problem, for example, M. Zukalova et al.
produced an oriented particle by polymer template method and the
resulted cell efficiency was higher than that of non-oriented
particle by 1.3% (Nano Letters, 5 (9), 1789-1792, 2005); J. M.
Macak et al. prepared a TiO.sub.2 nanotube with high aspect ratio
by anodization (Angewandte Chemie-International Edition, 44 (14),
2100-2102, 2005) and J. R. Jennings et al. produced a
photoelectrode from TiO.sub.2 nanotube and titanium substrate,
giving a electron collection efficiency of nearly 100% (Journal of
the American Chemical Society, 130 (40), 13364-13372, 2008), which
demonstrated that tubular or linear structures provide a better
diffusion direction for electrons; and K. Shankar et al. proved
that when a glass substrate was used instead, the cell efficiency
would reached 6.1% (Nano Letters, 8 (6), 1654-1659, 2008).
Nevertheless, the structure of nanotube and the like did not
provide sufficient dye-loading, so the other structures derived
from nanoparticles were still under research and development.
[0009] Another way to solve the low dye-loading problem was to use
the structure called TiO.sub.2 beads (see D. H. Chen et al.,
Advanced Materials, 21 (21), 2206, 2009 and Y. J. Kim et al.,
Advanced Materials, 21 (36), 3668, 2009). The TiO.sub.2 bead with
submicron-meter size had the following advantages: (1) this bead
dramatically increased light harvesting efficiency because its size
was large enough for Mie scattering, so the light route in the
photoelectrode lengthens and dye loading increased; (2) this bead
had a large surface area, which helped dye loading; (3) TiO.sub.2
bead had regular mesopores that increased electron transfer and
helped mass transfer of electrolyte. However, this two-layer
photoelectrode was only applied to rigid DSCs, not introduced into
flexible dye-sensitized solar cells (FDSCs). This was because there
were less contacts between large size TiO.sub.2 beads and the
substrate, so the photoelectrode was not well-attached on the
substrate, and this highlighted the disadvantage of FDSCs. In
recent studies, the best cell efficiency of the flexible
low-temperature glass DSCs using TiO.sub.2 beads was 6.3% (S. H.
Jang et al., Electrochemistry Communications, 12 (10), 1283-1286,
2010). TiO.sub.2 was not used in the general flexible plastic
substrates because the plastic substrates could only be processed
at 150.degree. C. or less and they could not bear the high
temperature treatment for removing organic compounds and sintering
TiO.sub.2 beads on the traditional rigid substrates (about
450.degree. C.). Therefore, the DSCs using TiO.sub.2 beads had low
electron collection efficiency and reduced cell efficiency.
SUMMARY OF THE INVENTION
[0010] The inventors were the first to use mesoporous titania beads
for manufacturing the photoelectrode of cells, and they
surprisingly found that the anatase TiO.sub.2 comprised in the
mesoporous titania beads and the oriented attachment between
crystal grains increased electron diffusion. In addition, the
TiO.sub.2 beads with submicron-meter size of the present invention
resulted in excellent light scattering. With these advantages, the
titania bead of the present invention can be used to give high
efficiency cells.
[0011] One object of the present invention is to provide a
photoelectrode comprising a titania layer composed of a mesoporous
titania bead, and said mesoporous titania bead comprises anatase
titania, which provides excellent light scattering and increases
dye-loading.
[0012] Another object of the present invention is to provide a
method for preparing the photoelectrode, wherein a titania layer
composed of a mesoporous titania bead is formed on a substrate.
[0013] To achieve these objects, the present invention provides a
photoelectrode, comprising (1) a substrate; and (2) a titania layer
composed of a mesoporous titania bead having a diameter of 200-1000
nm, specific surface area of 50-100 m.sup.2/g, porosity of 40-60%,
pore radius of 5-20 nm, pore volume of 0.20-0.30 cm.sup.3/g, and
the titania comprised in the bead is anatase titania.
[0014] In a preferred embodiment, said mesoporous titania bead has
a diameter of 500-1000 nm; and more preferably, 750-1000 nm.
[0015] In a preferred embodiment, said mesoporous titania bead has
a porosity of 50%.
[0016] In a preferred embodiment, the titania layer has a thickness
of 5-10 .mu.m; more preferably, 7.5-8 .mu.m.
[0017] In a preferred embodiment, said substrate is a metal
substrate, or a transparent non-conductive substrate covered by a
transparent conductive film. Preferably, said transparent
non-conductive substrate is a plastic or glass substrate, and said
transparent conductive film is ITO, FTO or other transparent
conductive oxide (TCO) film; more preferably, said plastic
substrate is PEN or PET substrate; and most preferably, the
substrate of the present invention is ITO-PEN substrate, ITO-glass
substrate, FTO-PEN substrate, titanium substrate or stainless steel
substrate.
[0018] In a preferred embodiment, said mesoporous titania bead is
prepared by the following steps:
[0019] (1) adding a steric agent and a titanium-containing
precursor into ethanol to proceed sol-gel reaction and give a
sol-gel product, wherein the molar ratio of said steric agent:said
titanium-containing precursor:ethanol is 0.1-1:1:200-300; and
[0020] (2) heating said sol-gel product in water at 120-200.degree.
C. for 1-24 hours to obtain the mesoporous titania bead.
[0021] In a preferred embodiment, said steric agent is a tertiary
amine; more preferably, said steric agent is selected from
hexamine, trimethylamine ((CH.sub.3).sub.3N), quinoline
(C.sub.9H.sub.7N), isoquinoline (C.sub.9H.sub.7N) or
methyldiethylamine (CH.sub.3N(CH.sub.2CH.sub.3)); and most
preferably, said steric agent is hexamine.
[0022] In a preferred embodiment, said titanium-containing
precursor is selected from titanium tetraisopropoxide, titanium
tetrachloride, titanium trichloride, ethyl orthotitanate or
Ti(OC.sub.4H.sub.8).sub.4; and most preferably, said
titanium-containing precursor is titanium tetraisopropoxide
(TTIP).
[0023] In a preferred embodiment, said step (2) is preferably
conducted at a temperature of 160-200.degree. C.; more preferably,
at 200.degree. C.
[0024] In a preferred embodiment, the method further comprises
adding a salt into said ethanol in step (1) to adjust ionic
strength to 1.times.10.sup.-4-32.times.10.sup.-4; more preferably,
said salt is selected from KCl, LiCl, KCl, LiF, NaF, KF, LiBr,
NaBr, KBr, LiI, NaI, KI, CsCl, CsI, CsBr, KNO.sub.3; and most
preferably, said salt is KCl.
[0025] In a preferred embodiment, said titania layer increases
scattering efficiency and used as a scattering layer.
[0026] In a preferred embodiment, a titania nanoparticle layer is
further comprised between said substrate and said titania layer;
preferably, said titania nanoparticle layer has a thickness of 3-5
.mu.m.
[0027] In a preferred embodiment, said titania nanoparticle layer
is composed of a titania nanoparticle, not composed of said
mesoporous titania bead; more preferably, said titania nanoparticle
of the titania nanoparticle layer is P25, ST-01, ST-21, ST-31,
TTO-55S or ST-30L.
[0028] In a preferred embodiment, said photoelectrode is used for
manufacturing a cell.
[0029] The present invention also provides a method for preparing
the above-mentioned photoelectrode, comprising:
[0030] (1) providing a substrate;
[0031] (2) coating a mesoporous titania bead on said substrate to
obtain a coated layer, in which said bead has a diameter of
200-1000 nm, specific surface area of 50-100 m.sup.2/g, porosity of
40-60%, pore radius of 5-20 nm, pore volume of 0.20-0.30
cm.sup.3/g, and the titania comprised in the bead is anatase
titania; and
[0032] (3) pressing the coated layer from step (2) under room
temperature to obtain said titania layer.
[0033] In a preferred embodiment, said substrate provided in the
above-mentioned method is a metal substrate, or a transparent
non-conductive substrate covered by a transparent conductive film.
Preferably, said transparent non-conductive substrate is a plastic
or glass substrate, and said transparent conductive film is ITO,
FTO or other transparent conductive oxide (TCO) film; more
preferably, said plastic substrate is PEN or PET substrate; and
most preferably, the substrate is ITO-PEN substrate, ITO-glass
substrate, FTO-PEN substrate, titanium substrate or stainless steel
substrate.
[0034] In a preferred embodiment, the above-mentioned method
further comprises the following step between step (1) and step (2):
coating a titania nanoparticle on said substrate to obtain a
titania nanoparticle layer, and said titania nanoparticle is not
said mesoporous titania bead; preferably, said titania nanoparticle
of the titania nanoparticle layer is P25, ST-01, ST-21, ST-31,
TTO-55S or ST-30L.
[0035] In a preferred embodiment, the above-mentioned method is
applied to cell manufacture.
[0036] The present invention has proved that the properties of
titania, such as crystallinity, surface oxygen vacancy
concentration and the like, affect diffusion and life span of
electrons, thereby affecting charge collection efficiency. And, the
size of titania bead apparently affects the efficiency of light
harvesting and electron injection, thereby affecting the cell
efficiency. The mesoporous titania bead, or the mesoporous titania
bead prepared by the method of the present invention, has a proper
size, good crystallinity and low surface oxygen vacancy
concentration. Moreover, it is also potential to be used as a
scattering layer, which is suitable for manufacturing
photoelectrode of cells, and enhancing cell efficiency.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] FIG. 1(A) shows the XRD diffraction diagrams of the sol-gel
products (S) obtained by using different amount of steric agent.
FIGS. 1(B)-1(D) show the XRD diffraction diagrams of the titania
products of the present invention (H). The first number after the
letter "H" represents the amount of steric agent, and the second
number represents the water-heating temperature.
[0038] FIG. 2 shows the HRTEM image of the mesoporous titania bead
prepared by using 0.75 g steric agent and heating at 200.degree. C.
in water-heating treatment in the present invention.
[0039] FIG. 3(A) shows the XRD diffraction diagrams of the titania
beads prepared by using different amount of steric agent and heated
at different temperature in water-heating step in the present
invention. FIG. 3(B) shows the XRD diffraction diagrams of the
commercial titania powders, P25 and ST41.
[0040] FIG. 4 shows the SEM images of the titania products prepared
by using (A) 0.25 g, (B) 0.50 g, (C) 0.75 g of steric agent and
heated at 200.degree. C. in water-heating step in the present
invention.
[0041] FIG. 5(A) shows the schematic illustration of photoelectrode
comprising a scattering layer and a titania nanoparticle layer.
FIG. 5(B) shows the schematic illustration of photoelectrode
comprising single titania layer. FIG. 5(C) shows the amplified
schematic illustration of photoelectrode composed of the commercial
titania P25 and the comprising titania beads of the present
invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0042] All scientific terms hereinafter are given their ordinary
meaning in the usage of the field of the invention, unless the text
of the patent makes clear that a term is used with a special
meaning.
[0043] The term "titania layer" used herein refers to a TiO.sub.2
layer prepared by the mesoporous titania beads of the present
invention, which is able to increase scattering efficiency and used
as a scattering layer. The titania layer has a thickness of 5-10
.mu.m, preferably, 7.5-8 .mu.m.
[0044] The term "titania nanoparticle layer" used herein refers to
a TiO.sub.2 layer prepared by titania nanoparticles, and said
titania nanoparticles are not the mesoporous titania beads of the
present invention or the mesoporous titania beads prepared by the
method of the present invention. The titania nanoparticle can be a
commercial nanoparticle, such as P25, ST-01, ST-21, ST-31, TTO-55S
and ST-30L, and the titania nanoparticle layer has a thickness of
3-5 .mu.m.
[0045] The term "substrate" used herein refers to a conductive
substrate, comprising but not limit to: a metal substrate, and a
transparent non-conductive substrate covered by a transparent
conductive film. Preferably, said transparent non-conductive
substrate covered by a transparent conductive film is a plastic or
glass substrate covered by a transparent conductive film. More
preferably, said transparent conductive film is ITO, FTO or other
transparent conductive oxide (TCO) film; and said plastic substrate
is PEN or PET substrate. The examples of the substrate used in the
present invention are ITO-PEN substrate, ITO-glass substrate,
FTO-PEN substrate, titanium substrate, stainless steel
substrate.
Preparation of the Titantia Products of the Present Invention
[0046] The titania products of the present invention were prepared
by a novel two-step process, comprising the first sol-gel reaction
step, and the second water-heating treatment step.
(1) Sol-Gel Reaction
[0047] First, 0.25 g, 0.50 g or 0.75 g of the steric agent,
hexamine (Riedel-de haen, 99.5%), was added into 200 mL of ethanol
(J-T baker, 99.9%), and stirred with a magnetic bar. Several
minutes later, 1 mL KCl ionic solution (0.1M) prepared by solid KCl
(SHOWA, 99.5%) was added into hexamine solution in ethanol to
adjust the ionic strength. Several minutes later, hexamine is
dissolved completely, and 4.4 mL of the titanium-containing
precursor, titanium tetraisopropoxide (TTIP) (Acros, >98%) was
added to start hydrolysis reaction, and the solution was turned
from transparent into white in minutes, which showed the proceeding
of condensation reaction. The solution was further stirred for
several minutes and stood for one day to complete the sol-gel
reaction. On the next day, the solution was filtered and dried, and
ground to give an amorphous white powder (TiO.sub.x), which was
named as a sol-gel product hereinafter.
(2) Water-Heating Treatment
[0048] 0.4 g of the sol-gel product obtained from the previous step
was added into 25 mL of deionized water and stirred for several
minutes, and then the mixture was placed in autoclave and stayed at
120.degree. C., 160.degree. C. or 200.degree. C. for 6 hours to
proceed water-heating treatment. After that, the solution was
filtered and dried to obtain a crystallized white powder, namely,
the titania product of the present invention.
Preparation of Photoelectrode
[0049] The titania product of the present invention and a
commercial titania powder P25 (Degussa) were used for the following
preparations.
[0050] First, a titania slurry was prepared. The above-mentioned
two titania had different surface characteristics, so different
formulations were used for their preparations: 0.6 g of P25 powder,
100 .mu.L of acetic acid (J-T baker, 99.9%), 0.5 mL of deionized
water, 2.5 mL of ethanol and 4 mL of tert-butanol (Merck, >99%)
were mixed, and stirred and sonicated alternating to obtain a
homogeneous and thick P25 slurry. In addition, 0.3 g of the titania
product of the present invention, 1.5 mL of ethanol and a trace of
HCl (Aldrich, 37%) were mixed, then the titania slurry of the
present invention was prepared by the steps the same as the
previous description.
[0051] An appropriate amount of the titania slurry of the present
invention (or P25 slurry) was dropped on a ITO-PEN substrate, and
spin-coated by a two-step spin-coating process: the first step was
proceed at 700 rpm for 20 seconds, and the second step wad proceed
at 1500 rpm for 20 seconds. After that, the coated substrate was
dried naturally. The spin-coating process was repeated until the
titania coating has a desired thickness, and then the coating was
scraped into a size of 4.times.4 mm square (0.16 cm.sup.2). Then
the pressing step under room temperature was taken, which means a
pressure of 50 kg/cm.sup.2 was given in a direction from the
titania coating to the ITO-PEN substrate for 5 minutes to enhance
the adherence between the photoelectrode and the ITO-PEN substrate
and the connection between the titania beads of the present
invention. At last, a photoelectrode (anode) comprising a titania
bead layer was obtained.
Preparation of Dye-Sensitized Solar Cell
[0052] Dye-sensitized solar cell was practiced as the embodiment of
the present invention, in which N719 (Solaronix) was used as the
dye comprised in the cell. 0.05 g of solid N719 was added into 100
mL of ethanol, and stirred and sonicated to obtain a N719 solution
having a concentration of 5.times.10.sup.-4 M, then the solution
was aliquoted and stored in the dark.
[0053] The obtained photoelectrode was soaked into the N719
solution for about one day, so the time was sufficient for dye to
be loaded on the surface of the titania product of the present
invention. After soaking, the photoelectrode was removed and soaked
into ethanol for about 10 minutes in order to remove the extra dye
aggregates. After that, the photoelectrode was removed and dried,
and ready for cell assembly.
[0054] A counter electrode (cathode) was prepared separately. A
vacuum platinum coater (JEOL 1600) was used to coat Pt on an
ITO-PEN substrate with a current of 20 mA for 200 seconds. And, an
electrolyte was prepared by MPN (Alfa Aesar, 99%) as a solvent, and
0.1M LiI (Aldrich, 99.99%), 0.05M I.sub.2 (Aldrich, 99.999%), 0.5M
TBP (Aldrich, 99%) and 0.6M DMPII (Solaronix).
[0055] At last, the dye-sensitized solar cell was assembled. A
spacer with pores (Surlyn) and having a thickness of 60 .mu.m and a
width of 0.6 cm was placed on the substrate of the photoelectrode,
and then covered by the counter electrode, so that the two pores on
the spacer were located on the diagonal line of the photoelectrode
for injecting electrolyte therein. When all elements were set at
the correct positions, the photoelectrode, spacer and counter
electrode were fixed by clamps and heated to melt the spacer and
adhere the upper and lower electrodes. The assembly was then cooled
naturally and then the electrolyte was injected. After electrolyte
injection, the pores of the spacer were sealed to avoid the
evaporation of electrolyte, which may cause degeneration of the
cell. When the cell assembly was completed, the cell was objected
to the determination of cell efficiency.
[0056] The following examples are provided to elucidate the present
invention, not to limit the scope of the present invention. Those
skilled in the art will recognize and understand them without
further explanation. All the references are hereby incorporated by
reference in its entirety herein.
EXAMPLES
Example 1
Analysis of the Titania Products of the Present Invention
[0057] A series of titania products were prepared by using
different amount of steric agent (0.25 g, 0.50 g or 0.75 g) and
heating at different temperature (120.degree. C., 160.degree. C. or
200.degree. C.) in water-heating treatment. These titania products
were labeled with the letter "H" to show that there were obtained
after water-heating treatment. For example, "H 0.25 120" represents
the titania product prepared by using 0.25 g of steric agent
(hexamine) and heating at 120.degree. C. in water-heating treatment
by the preparation method of the present invention.
I. Crystal Structure Analysis of the Titania Product of the Present
Invention
[0058] The titania products of the present invention were objected
to XRD phase identification and electron microscope analysis to
identify if these products had a long-range order crystal
structure, namely, the structure of anatase titania.
[0059] First, the titania products of the present invention were
separately dried at 60.degree. C. for one day to remove water and
volatile organic compounds, thereby reducing the noise of data.
Then the dried titania products prepared under a variety of process
parameters were separately detected by X-ray diffraction (XRD) in
Rigaku D-max XRD with Cu-K.sub.a radiation having a wavelength of
0.154 nm as the incident light, a scan range (two theta) of
20.degree. to 80.degree., and the scanning rate of 3.degree. per
minute.
[0060] FIG. 1(A) shows the XRD diffraction diagrams of the sol-gel
products obtained by using different amount of steric agent
(without water-heating treatment, labeled with the letter "S").
Regardless of the amount of steric agent, all diffraction diagrams
have no diffraction peak, and this shows that all sol-gel products
have an amorphous structure, not a long-range order structure.
[0061] In FIGS. 1(B)-1(D), the XRD diagrams show that the crystal
structures of all titania products of the present invention are the
same regardless of the amount of steric agent and the temperature
of water-heating treatment. After comparison with JCPDS 11-1272,
the peak of these XRD diagrams was identified as the diffraction
peak of anatase titania, in which the highest main peak was the
(101) face of anatase, and the two theta was located at
25.3.degree.. This result completely matches the JCPDS standard,
which shows that the titania product of the present invention is
anatase titania with a long-range order structure not stretched or
pressed by additional stress. In this study, the amount of steric
agent does not affect the crystal structure of the titania products
of the present invention because the diffraction peak strength, the
full width at half maximum (FWHM) and the diffraction angle of
these products are almost the same, and it also proves that
hexamine does not embed into the structure of TiO.sub.2 (O--Ti--O).
That is to say, hexamine is not involved in the chemical reaction,
and it is a true steric agent.
[0062] However, both the diffraction peak strength and FWHM are
different between the titania products obtained by heating
different temperatures in water-heating treatment. In FIG. 3(A),
for example, the diffraction diagrams of the titania products
obtained by using 0.75 g of steric agent and heating at different
temperatures in water-heating treatment are compared, and it is
found that when the temperature of water-heating treatment
increases, the strength of the (101) peak and other peaks
increases, and the FWHM narrows. In other words, the crystallinity
of the anatase titania powder increases when the temperature
increases. In addition, Debye-Scherrer equation is used to evaluate
the grain size of the titania products obtained under a variety of
process parameters, and it is found that when the temperature of
water-heating treatment increases, the grain size also increases
(14 nm, 18 nm, 20 nm)--these are size of monocrystalline
nanoparticles suitable for manufacturing photoelectrode of cells.
XRD values and grain sizes are shown in Table 1.
TABLE-US-00001 TABLE 1 XRD value and grain size of titania products
obtained under a variety of process parameters Grain size of
Diffraction angle two FWHM of (101) peak Sample theta of (101) peak
(.degree.) (101) peak (nm) H 0.25 120 25.30 0.572 14.2 H 0.25 160
25.28 0.464 17.5 H 0.25 200 25.30 0.407 20.0 H 0.50 120 25.32 0.581
14.0 H 0.50 160 25.31 0.462 17.6 H 0.50 200 25.30 0.404 20 H 0.75
120 25.29 0.576 14 H 0.75 160 25.32 0.455 18 H 0.75 200 25.30 0.411
20
[0063] The inventors observed the diffraction diagrams of these
products obtained after water-heating treatment, and found that
there were slightly rises and falls around 31.degree.. After
comparison with JCPDS 29-1360, it was identified as (121) face of
brookite, located at 30.8.degree. (data not shown). After
integration calculation, it was found the content of brookite in
all products was less than 1%, which did not shift the diffraction
peak of anatase, and so it could be recognized as a noise. In other
words, the powder obtained in this study can be recognized as pure
anatase, and this crystal structure is suitable for manufacturing a
photoelectrode of cells.
[0064] Moreover, JEOL JEM 2100F high-resolution transmission
electron microscope (HRTEM) was used to identify the crystal
structure of these powders. The HRTEM image of sample "H 0.75 200"
is shown in FIG. 2, in which the parallel black lines represent the
location of crystal faces. After magnification measurement, it is
found the distance between these faces (d) is 0.35 nm, the same as
that of the (101) face of anatase. The square represents the
connection of two grains, and it shows that the (101) faces of two
grains attach in the same direction, which means an oriented
attachment is formed. When the temperature of water-heating
treatment is 160.degree. C., an excellent oriented attachment is
obtained; and when the temperature of water-heating treatment is
low (120.degree. C.), the crystallinity of the product is low and
amorphous structure is formed (data not shown). The above HRTEM
data shows that the proportion of amorphous structure reduces when
the temperature of water-heating treatment increases, and this
result is fully supported by XRD results.
II. Crystal Structure Analysis of the Titania Layer of the Present
Invention
[0065] The titania products of the present invention and/or a
commercial titania powder (P25 or ST41) were used to prepare the
titania layers of photoelectrodes as foresaid, and Rigaku D-max2500
XRD was used to analyze their crystal structures. Rigaku D-max2500
XRD is similar to Rigaku D-max XRD, but it is equipped with
wide-angle function, and capable for glancing incident angle
diffraction, so the extra signals from the substrate can be
eliminated. Therefore, it is suitable for analyzing thin-film
samples, especially the thin-film samples having a thickness of 2
.mu.m or less.
[0066] The mesoporous titania beads prepared by using 0.75 g of
steric agent and heating at different temperature at the
water-heating treatment and the commercial titania powders ST41 and
P25 were independently used to prepare a layer made of TiO.sub.2 of
photoelectrode, and then objected to XRD analysis. The results are
shown in FIGS. 3A and 3B.
[0067] Similar with the foresaid crystal structure analysis, when
the temperature of water-heating treatment increases, the
crystallinity of the obtained mesoporous titania beads of the
present invention also increases. After comparison with JCPDS
21-1272, it was found that the mesoporous titania beads of the
present invention still had an anatase structure, and their
diagrams were same as the commercial anatase titania powder ST41.
ST41 had an obviously better crystallinity than the mesoporous
titania beads of the present invention, but it was a submicron
scale powder, and not suitable for manufacturing the photoelectrode
of cells. In addition, after comparison with JCPDS 21-1276, it was
also found that the commercial titania powder P25 has a proportion
of rutile structure with the main diffraction peak of (110) face at
27.4.degree., as described in the instruction sheet of manufacturer
(data not shown). So the P25 powder was also not suitable for
manufacturing the photoelectrode of cells. The XRD data and grain
size of these layers made of the titania products of the present
invention are listed in Table 2. From these data, it is clear that
the tendency of increased temperature in water-heating treatment
results in increased grain size is the same. Meanwhile, it also
proves that the crystal structure of the titania product of the
present invention does not change even after the titania product is
manufactured as a thin-film of photoelectrode.
TABLE-US-00002 TABLE 2 XRD value and grain size of the layers
prepared by the titania products of the present invention Grain
size of Diffraction angle two FWHM of (101) peak Sample theta of
(101) peak (.degree.) (101) peak (nm) H 0.25 120 25.30 0.572 14.2 H
0.25 160 25.28 0.464 17.5 H 0.25 200 25.30 0.407 20.0 H 0.50 120
25.32 0.581 14.0 H 0.50 160 25.31 0.462 17.6 H 0.50 200 25.30 0.404
20 H 0.75 120 25.29 0.576 14 H 0.75 160 25.32 0.455 18 H 0.75 200
25.30 0.411 20
[0068] The oxygen vacancy concentration can be calculated through
detecting the content of Ti.sup.3+ in the titania products of the
present invention (data not shown), thereby evaluating the
proportion of defects caused by oxygen vacancy concentration.
Relatively, surface oxygen vacancy carries positive charges, and
results in trap states to stop electron immigration. The inventors
have found that the beads prepared at a higher temperature in
water-heating treatment not only have an increased crystallinity of
anatase, but also have a reduced oxygen vacancy concentration,
which are advantageous for the following manufacture of
photoelectrode and cells.
III. Morphology Analysis of the Titania Product of the Present
Invention
[0069] JEOL 6701F scanning electron microscope (SEM) was used to
identify the shape and size of the titania products of the present
invention.
[0070] FIG. 4 shows the SEM images of the titania products of the
present invention prepared by using different amount of steric
agent and heating at 200.degree. C. in water-heating treatment, in
which (A) H 0.25 200 has an irregular shape; and (B) H 0.50 200 and
(C) H 0.75 200 have formed analogous spheres, also named as "bead"
herein. In addition, when the amount of steric agent increases, the
surface roughness of the beads reduces, which means the steric
agent helps the formation of sphere structure. The shape of H 0.75
200 is more closed to a sphere than H 0.50 200, and the distance
between the analogous spheres of H 0.75 200 is obviously increased.
This is also supported by the other titania products of the present
invention obtained under other process parameters. Comparing with
the amorphous sol-gel products (S) prepared by using different
amount of steric agent (data not shown), the titania products of
the present invention generally maintain the morphology of sol-gel
products (irregular or analogous sphere), but they are all
crystallized to be anatase titania, their atomic arrangement is
changed from disorder structure into long-range order structure,
and a new surface is formed. The temperature of water-heating
treatment affects the bead size, as shown in Table 3.
TABLE-US-00003 TABLE 3 Bead diameter of the titania products of the
present invention Size of sol-gel Size of beads Sample products
(nm) (nm) H 0.75 120 375 375 H 0.50 160 250 250 H 0.75 160 375 750
H 0.50 200 250 250 H 0.75 200 375 500 *The sizes of the mesoporous
titania beads of the present invention are diversely distributed,
and the data in Table 3 are average values. The real size range is
about .+-.50-.+-.100 nm.
[0071] The above results show that even the steric agent does not
affect the crystal structure, but its molecular structure provides
an effective space between the analogous sphere beads. Comparing
with the most well-known steric agent used in the art is
hexadecylamine (HAD), the steric agent used in the present
invention, hexamine, is a tertiary amine in which the nitrogen
atoms are shielded by carbon atoms, and not react with the
structure of titania (O--Ti--O), thereby avoiding extra doping and
disadvantageous influences to the crystal structure of the product
given after water heating treatment. Therefore, hexamine should be
a better steric agent. Furthermore, the amount of steric agent
affects the shape, size and surface structure of the titania
particles. If the amount of steric agent is not enough, irregular
nanoparticles will be formed as the final product, and the beads
will not be formed.
IV. BET Analysis of the Titania Product of the Present
Invention
[0072] Micromeritics ASAP2010 physisorption analyzer was used to
proceed Brunauer-Emmett-Teller analysis (BET analysis) to the
titania products of the present invention, in which the absorption
and desorption of nitrogen were detected under a vacuum degree of
10.sup.-3 ton or less and a temperature of 77K (liquid nitrogen) to
analyze the specific surface area, pore radius, pore volume,
porosity and the like of the samples. The data are shown in the
following Tables 4 and 5.
TABLE-US-00004 TABLE 4 BET analysis result of the titania products
of the present invention obtained by heating at different
temperatures in water-heating treatment Specific surface Pore
radius Pore volume Porosity Sample area (m.sup.2/g) (nm)
(cm.sup.3/g) (%) S 0.75 180 2.5 0.11 30 H 0.75 120 95 11.6 0.27 51
H 0.75 160 69 16.0 0.27 51 H 0.75 200 62 16.1 0.25 49 P25 55 9.7
0.13 34
TABLE-US-00005 TABLE 5 BET analysis result of the titania products
of the present invention obtained by using different amount of
steric agent Specific surface Pore radius Pore volume Porosity
Sample area (m.sup.2/g) (nm) (cm.sup.3/g) (%) S 0.25 182 2.4 0.10
28 S 0.50 180 2.5 0.11 30 S 0.75 180 2.5 0.11 30 H 0.25 200 63 16.5
0.26 50 H 0.50 200 62 17.7 0.27 51 H 0.75 200 62 16.1 0.25 49
[0073] Specific surface area affects two factors important to cell
efficiency, that is, the dye loading and light harvesting of
dye-sensitized solar cells. Generally speaking, nanoparticles have
greater specific surface area and can be applied to more
applications. From the above Tables 4 and 5, however, it is found
that the sol-gel products have a high specific surface area, but
they are amorphous and not suitable for cell applications. Usually,
pore radius has a negative correlation with specific surface area,
and blocks the mass transfer of dye and electrolyte. But the pores
(mesopore in the present invention) of the titania beads have
greater pore radius and volume than P25. For example, H 0.75 200 of
the present invention has a specific surface area similar with P25,
but its pore size and volume are almost twice than those of P25.
This is resulted from the difference in their structure. In
addition, the mesoporous titania bead of the present invention has
a porosity of about 50%, which is suitable for manufacturing
photoelectrodes.
[0074] From the data shown in Table 5, it is found that the amount
of steric agent does not obviously affect the specific surface area
and pore radius of the titania products of the present invention,
which means, it does not affect the morphology of the beads.
Additionally, the microscopic observation has proved that although
H 0.25 200 is a nanoparticle, but it has a pore volume similar with
that of beads. That is to say, although H 0.25 200 has an irregular
structure, it has mesopores.
Example 2
Preparation of Dye-Sensitized Solar Cells with an Electrode
Manufactured by Using the Titania Product of the Present Invention
and P25 Powder and Efficiency Analysis thereof
[0075] The dye-sensitized solar cells comprising a photoelectrode
shown in Table 6 were manufactured as foresaid. The structure of
these photoelectrodes is shown in FIG. 5(A), which is a well-known
structure of dye-sensitized solar cells, comprising two layers made
of titania, wherein the first one is scattering layer (bead layer)
and the second one is a titania nanoparticle layer (P25 layer). In
Table 6, photoelectrode A merely comprised a titania nanoparticle
layer composed of pure P25, no scattering layer was comprised.
Photoelectrode B comprised a titania nanoparticle layer composed of
pure P25 and a scattering layer composed by pure P25, so it was
substantively equal to a pure P25 nanoparticle layer of 8 .mu.m. In
photoelectrode C-G, the second layer was composed of the titania
products of the present invention, in which the second layer of
photoelectrodes C-F was prepared by coating the titania bead of the
present invention on photoelectrode A, and the second layer of
photoelectrode G was prepared by H 0.25 200 which was not in form
of bead, but in form of nanoparticle (irregular shape under SEM
observation). The labels of the titania products of the present
invention are as foresaid described.
[0076] The cell efficiency (.eta.) of the above-mentioned
dye-sensitized solar cells was measured by the standard method for
measuring dye-sensitized solar cell efficiency, in which solar
simulator was used with parameter set at AM 1.5 G to mimic the cell
expression under true sun light. In addition, a power supply was
used to provide an applied voltage to the dye-sensitized solar cell
of the present invention in order to detect the resulted
photocurrent. The applied voltage was changed to mimic the
expression of cell under load, thereby calculating the cell
efficiency (.eta.), as shown in Table 6.
[0077] Furthermore, the dye-loaded photoelectrodes were soaked in
an alkali solution (such like 0.1M NaOH in ethanol) for about 1
hour to deabsorb the dye, and the resulted solution was objected to
analysis by UV-vis spectrometer for calculating the dye loading.
The results are shown in Table 6.
TABLE-US-00006 TABLE 6 Result of titania layers of photoelectrode
prepared by using P25 powder alone or using the titania product of
the present invention and P25 powder 1.sup.st 2.sup.nd Bead Cell
layer layer size Dye loading efficiency .eta. Sample (3 .mu.m) (5
.mu.m) (nm) (.times.10.sup.-7 mol/cm.sup.2) (%) A P25 -- -- 0.87
3.21 B P25 P25 -- 2.37 4.29 C P25 H 0.75 120 375 4.85 4.57 D P25 H
0.75 160 750 4.64 5.01 E P25 H 0.75 200 500 4.52 5.48 F P25 H 0.50
200 250 4.48 4.84 G P25 H 0.25 200 NPs 4.32 4.55 NPs: nanoparticles
(not beads)
[0078] In Cells A-G, as shown in Table 6, it is found that Cell A
has the lowest efficiency (3.21%), and Cell E has the highest
efficiency (5.5%). The main difference between Cells A and B is the
thickness of photoelectrode, so the dye loading is obviously
different--Cell B has a greater dye loading, which is able to
produce more electrons and results in a better efficiency (4.29%).
The two-layer structures of Cells B-G have the same thickness of
photoelectrode, but Cells C-G with a second layer made by the
titania product of the present invention have a higher efficiency
than Cell B with a second layer made by P25 only. Particularly, the
cell efficiency of Cell E is higher than higher than Cell B by
nearly 30%, and it is 1.7 times of Cell A. These data show that the
scattering layer of photoelectrode prepared by the mesoporous
titania beads of the present invention dramatically increases the
cell efficiency.
[0079] Furthermore, the dye-loading of Cells C-G is about twice of
Cell B (data not shown), and this is related to the higher specific
surface area and pore volume of the titania products of the present
invention. Greater dye-loading means the cell is capable of
absorbing more light to produce more electrons. FIG. 5(C) is the
amplified schematic illustration of the P25 layer and the titania
layer of the present invention in Cells C-G. When the
particles/beads are normally piled up, the space between the
titania beads of the present invention is greater, which is easy to
accommodate dye or electrolyte, but the titania nanoparticles
comprised in the beads are contact and orientedly attached. The
photoelectrode using the mesoporous titania bead of the present
invention has about twice dye loading than that made of ST 41 that
is generally used for the scattering layer of photoelectrode (data
not shown).
[0080] Cells C-G using the titania beads of the present invention
does not have an apparent difference in dye loading, but they do
have an obvious difference in cell efficiency: the lowest is Cell G
(4.55%), and the highest is Cell E (5.48%). It shows that different
amount of steric agent and different temperature of water-heating
treatment give the titania products different crystallinity, bead
size and surface oxygen vacancy concentration in the present
invention, and all these characteristics affect cell
efficiency.
[0081] This example provides a two-layer titania structure prepared
by the mesoporous titania beads of the present invention and
commercial titania nanopowder P25 (i.e., bead layer and
nanoparticle layer), and the titania nanoparticle layer can be
prepared by any nano-scale titania powder.
Example 3
Preparation of Dye-Sensitized Solar Cells with an Electrode
Manufactured by Using the Titania Product of the Present Invention
Alone and Efficiency Analysis thereof
[0082] The dye-sensitized solar cells comprising a photoelectrode
shown in Table 7 were manufactured as foresaid, wherein the
structure of these photoelectrodes is shown in FIG. 5(B).
Photoelectrode O was composed of the nanoparticle H 0.25 200, which
was not in form of bead. Photoelectrodes H-N were prepared by using
the mesoporous titania bead of the present invention alone. Sample
B was the control. The labels of the titania products of the
present invention are as foresaid described.
TABLE-US-00007 TABLE 7 Result of titania layers of photoelectrode
prepared by using the titania product of the present invention
alone thick- Bead Cell Photo- ness size Dye loading efficiency
.eta. Sample electrode (.mu.m) (nm) (.times.10.sup.-7 mol/cm.sup.2)
(%) B P25 8 -- 2.37 4.29 H H 0.75 120 7.5 375 5.60 3.16 I H 0.75
160 2.7 750 1.90 2.63 J H 0.75 160 5.2 750 3.64 3.69 K H 0.75 160
7.8 750 5.48 4.03 L H 0.75 160 10.0 750 6.84 3.53 M H 0.75 200 7.6
500 5.28 4.92 N H 0.50 200 7.8 250 5.12 4.74 O H 0.25 200 7.8 NPs
4.96 4.56 NPs: nanoparticles (not beads)
[0083] In Cells I, J, K and L, which uses the same bead (H 0.75 160
with bead size of 750 nm) with different thickness of titania
layer, the best cell efficiency does not go to Cell L having the
thickest titania layer, but to Cell K having a thickness of 7.8
.mu.m; and the cell efficiency of Cell K is close to Cell B having
a photoelectrode prepared by pure P25 with an equal thickness (8
.mu.m). Regarding with Cells H-O prepared by the titania product of
the present invention alone, the lowest cell efficiency goes to
Cell H (3.16%), and the highest goes to Cell M (4.92%); and the
cell efficiency of Cell M is higher than Cell B of pure P25 by
nearly 15%. In addition, the dye loading of the mesoporous titania
beads of the present invention can be 2-3 times of P25 (Cell
B).
[0084] In the flexible cell applications, the best thickness of
titania layer is generally not over 10 .mu.m. Thus, it is obvious
that the mesoporous titania beads of the present invention can be
applied to the flexible cells, especially to dye-sensitized solar
cells.
Example 4
Preparation of Dye-Sensitized Solar Cells with an Electrode
Manufactured by Using the Mixture of the Titania Product of the
Present Invention and P25 Powder and Efficiency Analysis
thereof
[0085] The dye-sensitized solar cells comprising a photoelectrode
shown in Table 8 were manufactured as foresaid, wherein the
structure of these photoelectrodes is shown in FIG. 5(B).
Photoelectrodes Q-S were prepared by the mixture of H 0.75 160 and
P25 at a specific ratio into a layer with a specific thickness.
Photoelectrodes T-V were prepared by the mixture of one of the H
200 series and P25 at a specific ratio into a layer with a specific
thickness. Samples B and K were controls. The labels of the titania
products of the present invention are as foresaid described.
TABLE-US-00008 TABLE 8 Result of titania layers of photoelectrode
prepared by using the mixture of titania product of the present
invention and P25 TiO.sub.2 bead of Final Dye Cell the present bead
loading efficiency Sam- P25 invention thickness size
(.times.10.sup.-7 .eta. ple (wt %) (wt %) (.mu.m) (nm)
mol/cm.sup.2) (%) B 100 -- 8.0 -- 2.37 4.29 K -- 100 7.8 750 5.48
4.03 (H 0.75 160) P 75 25 7.5 375 3.08 2.97 (H 0.75 120) Q 25 75
7.0 750 4.50 1.88 (H 0.75 160) R 50 50 7.4 750 3.73 2.62 (H 0.75
160) S 75 25 7.7 750 2.95 3.01 (H 0.75 160) T 75 25 7.6 500 2.84
3.21 (H 0.75 200) U 75 25 7.5 250 2.72 3.00 (H 0.50 200) V 75 25
7.5 NPs 2.63 3.25 (H 0.25 200) NPs: nanoparticles (not beads)
[0086] In the preparation of Cells Q-S, the beads of H 0.75 160
(with bead size of 750 nm) were mixed with P25 with a specific
proportion of 75%, 50% and 25%, respectively. Comparing with Cell K
using pure H 0.75 160 as the photoelectrode, Cells Q-S have a
dramatically reduced cell efficiency. This shows that the mixtures
of the mesoporous titania bead of the present invention and P25
gave a cell efficiency lower than pure bead, and Cell S having a
lower bead content (25%) provides a relatively high cell efficiency
(3.01%). The dye loading increases when the bead content increases
(data not shown), which demonstrates that P25 does not fill in the
space between beads. However, the other mixture of a variety of
titania products of the present invention and P25 have similar cell
efficiency according to data shown in Table 8, which means the
interface between P25 and the titania products of the present
invention consumes electrons, and eliminates the difference between
these materials.
[0087] In summary, these examples clearly elucidate that the
present invention provides a two-step method for preparing a
mesoporous titania bead, and the mesoporous titania bead prepared
by the method. Said mesoporous titania bead increases cell
efficiency. When the thickness of the photoelectrode is 8 .mu.m,
the titania nanoparticle layer made by pure P25 increases cell
efficiency by 4.3%; the combination with a mesoporous titania bead
layer of the present invention increases cell efficiency by 5.5%,
which is about 30% higher; and the titania layer made by the
mesoporous titania bead of the present invention alone increases
cell efficiency by 5%, which is about 20% higher. From above, it
should be clear that a photoelectrode with higher crystallinity and
lower surface oxygen vacancy concentration helps electron diffusion
and reduces the recombination, thereby increasing electron
collection efficiency dramatically. In addition, although larger
bead provides higher light harvesting efficiency, but it also
causes more back-scattering, and the electron injection efficiency
reduces because the extra dye stays in the space between beads;
however, the increase of light harvesting is greater than the
reduce of electron injection efficiency, as well as the fast
electron diffusion resulted from anatase titania and the oriented
attachment, the cell efficiency is still higher than the
traditional technology. From the data of the present invention, the
best titania bead for photoelectrode has a bead size of 500 nm with
high crystallinity and low surface oxygen vacancy concentration
because it results in more back-scattering and good
dye-loading.
* * * * *