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 international journal of hydrogen energy xxx (xxxx) xxx

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High performance tubular protonic ceramic fuel

cells via highly-scalable extrusion process

Liangzhu Zhu a,c,*, Ryan O'Hayre a,**, Neal P. Sullivan b,***

a
Metallurgical and Materials Engineering Department, Colorado School of Mines, 80401, USA
b
Mechanical Engineering Department, Colorado School of Mines, 80401, USA
c
Ningbo Institute of Materials Technology & Engineering, Chinese Academy of Sciences, 315201, China

highlights

Up to 66 cm long straight green PCFC anode supports are extruded.

Tubular PCFC cells with dense electrolyte layer are fabricated.

Three emerging PCFC cathode materials, BSCF, BCFZY, and PBSCF are synthesized and compared.

Maximum power density exceeds 500 mW cm2 at 600  C using BCFZY and BSCF cathodes.

A short 2-cell stack delivers 2.3 W power output at 600  C.

article info abstract

Article history: We report an effective method to fabricate long, anode-supported tubular protonic ceramic
Received 10 March 2021 fuel cells (PCFCs) and test cells in single-cell and short-stack mode. Further, we use our
Received in revised form tubular PCFC platform to directly compare three high performance cathodes reported in
31 May 2021 literature: BaCo0$4Fe0$4Zr0$1Y0$1O3-d (BCFZY), Ba0$5Sr0$5Co0$8Fe0$2O3-d (BSCF), and PrBa0.5-
Accepted 4 June 2021 Sr0$5Co1$5Fe0$5O6-d (PBSCF) using indentical preparation methods, which can minimize ef-
Available online xxx fects from variation of materials either due to suppliers or subsequent processing and
testing from different research labs. Using a BCFZY cathode, the maximum power density
Kewwords: of our tubular PCFC reaches 164, 308, and 517 mW cm2 at 500, 550, and 600  C, respec-
PCFC tively. A 2-cell tubular short stack provides a total power of 2.3 W at 600  C with tube di-
Solid oxide fuel cell ameters of 0.82 cm and a total tube active length of 3.2 cm. At 600  C, the maximum power
Tubular density reaches, 534, 517, and 326 mw cm2 for the BSCF, BCFZY, and PBSCF cathodes,
Extrusion respectively. Under the same conditions, the BSCF-based cell shows the lowest total
Cathode resistance mostly due to the lowest ohmic resistance and modest polarization resistance.
The BCFZY-based cell has the lowest polarization resistance but larger ohmic resistance
leading to a slightly higher total resistance than BSCF. The PBSCF cell has an ohmic
resistance close to BSCF but a total polarization resistance much larger than either BSCF or
BCFZY cell which results in the lowest overall performance.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author. Ningbo Institute of Materials Technology & Engineering, Chinese Academy of Sciences, 315201, China.
** Corresponding author.
*** Corresponding author.
E-mail addresses: zhuliangzhu@nimte.ac.cn (L. Zhu), rohayre@mines.edu (R. O'Hayre), nsulliva@mines.edu (N.P. Sullivan).
https://doi.org/10.1016/j.ijhydene.2021.06.018
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Zhu L et al., High performance tubular protonic ceramic fuel cells via highly-scalable extrusion process,
International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.06.018
2 international journal of hydrogen energy xxx (xxxx) xxx
Introduction
Protonic ceramic cells (PCCs) including protonic ceramic fuel
cells (PCFCs) and protonic ceramic electrolyser cells (PCECs)
have rapidly attracted attention in the past ten years. PCCs
offer several intriguing advantages over their conventional
oxygen ion conducting solid oxide cells (SOCs) predecessors,
including higher theoretical fuel utilization under fuel cell
mode, higher coking resistance, the ability to produce nearly
dry, pure H2 under electrolysis mode, and the ability to oper-
ate at temperatures typically 200  C lower than conventional
SOCs. These advantages result in lower materials cost, longer
device lifetime, and the potential to directly match their
electrochemical operation to the temperature window of
several key thermochemical processes [1e8].
High protonic conductivity of ~0.03 S cm1 at 600  C has
been measured in both BCZYYb7111 (BaCe0$7Zr0$1Y0.1Yb0.1-
O3ed) and BCZYYb4411 (BaCe0$4Zr0$4Y0.1Yb0.1O3ed) electrolytes
[3,9]. Maximum power densities exceeding 600 mW cm2 at
600  C have also been reported by a few studies [3,5,6]. While
these studies have led to promising performance for PCC vs.
SOC lab-scale button cells at lower temperatures, progress in
large-scale PCC development has lagged. In general, SOC
commercialization has focused on either planar or tubular
geometries [10e16]; the same geometries are also preferred for
PCC scale-up and stacking. However, PCC scale-up is
hampered by several important issues. For example, based on
our experience sintering barium perovskite type proton con-
duction materials, we have found these materials react
considerably with substrates such as low-cost alumina or
zirconia plates, necessitating more costly solutions for vol-
ume manufacturing. Another difficulty in fabricating large
planar PCC stack assembly lies in the thermal expansion
mismatch between the metal alloy interconnects and the PCC
due to thermo-chemical expansion effects, i.e., zero or even
negative expansion can occur around the PCC working tem-
perature (normally 600  C) [17]. This behavior severely chal-
lenges planar PCC stack stability and operation, particularly
during start up and shut down.
Many of the issues challenging planar PCC scale-up and
stacking, however, can be potentially mitigated by pursuing a
tubular PCC approach. Firstly, tubular PCC parts can be hang-
fired, therefore eliminating the need for a setter, which miti-
gates reactivity and results in better quality control in cell
fabrication. Secondly when assembled into stacks, tubular
PCCs are mostly free from metal alloy interconnects and the
geometry minimizes stress concentration risers and the ef-
fects of thermo-chemical expansion. Additionally, the tubular
geometry generally provides higher mechanical strength than
a planar geometry of the same wall thickness. Finally, the
tubular PCC geometry better facilitates integration with
additional catalysts for applications where a second-step
thermochemical reaction is coupled to the electrochemical
cell process, such as catalytic membrane reformer applica-
tions or the in-situ synthesis of ammonia or other value-
added chemicals [18,19]. Therefore, the fabrication of large
tubular PCCs may offer a promising avenue for commerciali-
zation. So far, however, relatively few studies have pursued
the tubular PCC approach.
Please cite this article as: Zhu L et al., High performance tubular protonic ceramic fuel cells via highly-scalable extrusion process,
International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.06.018
Different methods have been developed for tubular PCFC
fabrication [20e27], among which the phase inversion process
is used for most current lab-scale tubular PCFC demonstration
efforts. This process in general is suitable for making hollow
structures with finger-like or aligned pores by exploiting self-
assembling “polymer-rich” (solid phase) and “polymer-poor”
phases. The “polymer rich” network phase aggregates the
solid ceramic particles that will be retained after firing, while
the “polymer-poor” phase dissovles in a nonsolvent liquid
phase which is usually water, leaving an aligned pore struc-
ture [22,28e30]. Since the outer surface first sees the non-
solvent liquid during the phase inversion proces, aligned
pores generally form with an orientation perpendicular to
outer surface. Although vertical pores are desired in fuel cell
electrodes to facilitate mass transport, this structure usually
results in poor mechanical strength. In both cases, pore
orientation develops due to either the one-dimensional
chemical gradient of non-solvent concentration (i.e., water
concentration at the outer surface of a casted tube in the
phase inversion process) or the one-dimensional temperature
gradient in the solvent. Such aligned pores can lead to me-
chanical issues due to the highly anisotropic structure and
may ultimately lead to cell failure, thereby diminishing the
advantages associated with improved mass transport. This is
likely one of the reasons that such processes have not been
widely adopted for SOC scale-up/volume production. From a
manufacturability perspective, extrusion may therefore pro-
vide a better route towards large-scale production for both
tubular SOC and tubular PCC fabrication. Unfortunately, there
is very limited work on the extruded PCCs, and when extru-
sion has been used for tubular PCC production, the fabrication
details are often absent [19,26].
In addition to the preference for hard-to-scale phase-
inversion and slip-casting processes, most prior tubular PCFC
studies have deployed earlier-generation LSM (La1-xSrxMnO3-d)
or LSCF (La1-ySryCo1-xFexO3- d) cathodes. Very few studies
have yet sought to implement some of the more recently
advanced PCC-specific cathodes such as BCFZY or PBSCF.
Thus, in addition to developing a scalable extrusion-based
PCC fabrication protocol in this work, we also seek to imple-
ment and compare three of these emerging cathode materials
(BCFZY, PBSCF, and BSCF) using a single long tubular PCC
parent cell to facilitate direct comparison under well-
controlled testing conditions. We also demonstrate the per-
formance of a short-stack 2-tube bundle. The ultimate goal of
this study is to bring the tubular application of PCCs one step
closer to fruition and to provide a rational comparison of
currently developed PCC cathode materials in order to accel-
erate the development of PCC technology.
Materials and methods
Anode support extrudate preparation
Anode support powder was prepared by ball milling NiO and
BaCe0$7Zr0$1Y0.1Yb0.1O3-d (BCZYYb) at a weight ratio of 65:35.
The BCZYYb precursor was directly added as mixture of
BaCO3, CeO2, ZrO2, Y2O3, and Yb2O3 according to the set stoi-
chiometry via in-situ solid state reactive sintering process
 international journal of hydrogen energy xxx (xxxx) xxx
[1,5]. 20 wt% of corn starch and 3 wt% of methyl cellulose were
added as pore former and water soluble binder respectively.
The resulting powder precursor was blended by ball milling
for 15 h. The powder after ball milling was stored for subse-
quent extrusion processes.
Anode support extrusion
To extrude the anode support tubes, the as-prepared anode
support powder was mixed with water and firstly extruded
using a kitchen type pasta extruder (due to lack of laboratory
pug mill). This step generates a ceramic clay with suitable
viscosity for further extrusion. The ceramic clay was then
shaped into rectangular bricks, sealed and aged for 16 h before
final tube extrusion. For the final extrusion, the aged clay was
loaded into the pressing chamber, slightly vacuumed, and
slowly extruded (See Fig. S1 in Supplementary Information
(SI)). The extruded green tubes were firstly dried inside an
alumina tube with an inner diameter slightly larger than the
outer diameter of the extruded tube at 30  C for about 3 h
followed by additional drying at 80  C for 5 h. This drying
procedure produced straight tubes with good mechanical
strength to facilitate further handling.
Electrolyte and cathode powder preparation
To improve electrolyte density, nanosize BCZYYb powder was
prepared by a sol-gel process using procedures similar to those
reported in previous studies [4,31]. Briefly, citric acid and EDTA
were added into distilled water under stirring. Nitrates of
Ba(NO3)2, Ce(NO3)3$6H2O, ZrO(NO3)2 (35 wt.-% in dilute nitric
acid), Y(NO3)36H2O, and Yb(NO3)3$5H2O were added under
stirring. 1 wt% of NiO was added directly to the sol in the form
of Ni(NO3)2$6H2O as a sintering agent. NH3.H2O was slowly
added at a ratio of 1000 ml NH3$H2O per mole of citric acid or
EDTA, after which the solution became dark red and trans-
parent. The molar ratio of EDTA: citric acid: total metal ions was
1.5 : 1.5: 1, with a pH of ~9. The solution was placed on a 250  C
hot plate under stirring to form a gel. The gel was dried at 150  C
for 24 h to form a black, porous, charcoal-like precursor. The
solid precursor was manually crushed and slightly ground, and
then ball milled with yttria-stabilized zirconia media and iso-
propanol for 24 h. Following milling, the black charcoal slurry
was dried at 90  C for 12 h. The powder was then calcined at
800  C for 10 h, and then wet ball milled in isopropanol with
YSZ media for 72 h to further reduce the particle size. The slurry
was then dried for 24 h at 90  C and stored for electrolyte slurry
preparation. The three cathodes, Ba0$5Sr0$5Co0$8Fe0$2O3-d (BSCF),
BaCo0$4Fe0$4Zr0$1Y0$1O3-d, PrBa0.5Sr0$5Co1$5Fe0$5O6-d (PBSCF),
were synthesized in the same way (without nickel nitrate
addition) but calcined at lower temperature and shorter time
(600  C for 5 h) to minimize grain growth.
Full-cell fabrication
Due to limited furnace size, the dried long green tubes were
cut into shorter tubes. A pair of small holes were made at the
top of each tube to facilitate hang firing using platinum wires
for tube suspension. These shorter green tubes were debin-
dered and firstly sintered at 1200  C for 2 h. To apply the
Please cite this article as: Zhu L et al., High performance tubular protonic ceramic fuel cells via highly-scalable extrusion process,
International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.06.018
3
electrolyte layer, the BCZYYb nano-powder was mixed with a
binder (5 wt % V-006 in alpha-terpineol) and a dispersant
(20 wt% Solsperse 28,000) in alpha terpineol to prepare a slurry
using a method reported previously but with modified slurry
composition [4]. The weight ratio was set as electrolyte:
binder: dispersant ¼ 5:1:2. The mixed electrolyte slurry was
then brush-applied to the outer surface of the pre-sintered
anode support tube. After electrolyte application, the tubes
were hang-fired by platinum wires inside open alumina tubes
at 1450  C for 10 h. After sintering, a center region of each tube
was brushed painted with one of the three cathode pastes. All
three cathodes pastes were prepared by mixing 4 g of cathode
powder, 1 g of BCZYYb (synthesized via solid state reaction
and calcined at 1400  C for 10 h), 0.4 g 5 wt % V-006 in alpha-
terpineol, and 1 g of 20 wt% Solsperse 28,000 [4]. The non-
coated region of each tube was covered by tape to ensure an
accurate electrode area. After application of cathode paste,
the tubes were fired at 900  C for 5 h, completing the cell
fabrication process. The tubes had a final outer diameter of
~0.82 cm. For single cells, the cathode length is 0.5 cm making
the active cathode area of ~1.29 cm2. For short stack test, each
tube has a cathode length of 1.6 cm, making the total active
area for the two tubes in series connection 8.24 cm2.
Cell testing assembly
After cathode application and firing, a thin layer of Au paste
was applied on top of the cathode to improve current collec-
tion. Ag wire was then wrapped on top of the Au layer, short
Ag grids were manually painted across the center Ag wire
extending to two edges of cathode area, as shown in Fig. S2a
(See SI). A thin Au paste coating was also to the anode side
(inner anode chamber) and four Ag grids were painted at
about 90 interval using a silver paste (DAD-87). A cylindrical
Ag mesh was gently inserted into the anode chamber with two
wire leads extending out for electrical connection and mea-
surement. The space inside the cylindrical Ag mesh was filled
with porous insulation wool to secure good electrical contact.
Finally, the tubular cell with wire leads was mounted in a
specially designed test fixture (Fig S2a and 2b). The tube ends
were sealed using Ceramabond (552-VFG). A piece of quartz
tube was placed roughly co-axially with the ceramic cell. A
thin air tube was inserted into the center zone of the quartz
tube whose open ends were blocked by insulation wool.
Lastly, a thermocouple was placed beside the tubular cell. This
completed the initial test assembly. The whole assembly was
then loaded to a vertical furnace and heated up for cell testing.
For the short stack demonstration, the cells were connected in
series and tested similarly except no forced air flow was
provided.
Characterization and measurement
A Keithley 2000 multimeter was used to monitor cell voltage.
Solartron 1260 and 1287 were used for electrochemical mea-
surements and analyses. 4-probe and 2-probe measurements
were used for single cell and short stack testing, respectively.
After testing, cell cross section imaging was conducted using a
JEOL 7000 Field-Emission Scanning Electron Microscope
(FESEM). Structural information for the synthesized cathode
4 international journal of hydrogen energy xxx (xxxx) xxx
materials was acquired by a PANalytical PW3040 X-ray
Diffractometer.
Results and discussion
Cell macro- and micro-structure
Fig. 1a shows an example of an extruded NiO/BCZYYb green
tube reaching the maximum extrudable length in this work,
Fig. 1 e Photographs documenting the tubular PCC
fabrication process used in this study. (a) a 66 cm long
green tube after extrusion. (b) a pre-sintered short tube
with applied electrolyte layer on the outer surface. (c) hang-
firing apparatus for half-cell sintering. (d) Sintered half-cell
with electrolyte layer on the outer surface. (For
interpretation of the references to color in this figure
legend, the reader is referred to the Web version of this
article.)
Please cite this article as: Zhu L et al., High performance tubular protonic ceramic fuel cells via highly-scalable extrusion process,
International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.06.018
about 66 cm long. The extruded tube is reasonably, although
not perfectly straight, and is sufficiently long for large scale
tubular stack application. Due to limited size of the sintering
furnaces available in our lab, we cut these long tubes into
shorter tube segments for firing and cell testing. Fig. 1b shows
a representative unfired tube segment with applied electrolyte
layer. Fig. 1c shows the hang-firing process used for this study
which eliminates contact of the cell with the substrate.
Finally, Fig. 1d shows a fully-sintered half-cell. The visible
reflection of light serves as the first evidence of a dense elec-
trolyte layer.
Fig. 2aed provide representative SEM cross-section images
from a tested cell at various magnifications for the anode
support/electrolyte/cathode sandwiched structure. The cell
consists of a ~650 mm thick Ni/BCZYYb anode support (after
reduction), a ~15 mm thick BCZYYb electrolyte layer, and a
~15 mm thick BCFZY cathode. The anode support shows evenly
distributed pores of less than 10 mm diameter facilitating mass
transport of fuel (Fig. 2a). As shown in Fig. 2b, the electrolyte
layer is dense with a few isolated pores of submicron diameter
which do not affect the cell open circuit voltage (OCV). The
anode support shows nanosize exsolved Ni particles on the
grains of the percolating electrolyte phase (Fig. 2c). In-situ
nano-catalyst formation (exsolved and catalytically active Ni
nanoparticles that decorate the protonic ceramic phase in the
cermet anode) has been previously reported by several groups
and contributes to high performance as well as high coking
resistance against hydrocarbon fuels [5,32e34]. Even after
testing, the BCFZY cathode remains highly homogeneous and
uniform with fine particle size and porosity (~100 nm), and the
cathode/electrolyte interface remains coherent without signs
of fracture or delamination (Fig. 2d).
Fuel cell performance
We first establish the baseline performance of our tubular cell
using the BCFZY cathode, as we have previous experience
applying and testing this cathode on planar PCC and SOC ar-
chitectures [1,4,5,35]. Fig. 3 shows the performance of the
BCFZY-based cell under dry hydrogen and humidified air from
500 to 600  C. The cell yields OCVs of 1.13, 1.11, and 1.08 V and
maximum power densities (MPDs) of 164, 308, and
517 mW cm2 at 500, 550, and 600  C, respectively. Represen-
tative performances from BSCF cathode at the same temper-
atures are shown in Fig.S3. To the author's knowledge, this
performance represents the highest tubular PCFC perfor-
mance so far reported on highly scalable extrusion process at
the same temperature. The performance however are lower
than that reported by Chen et al. [20,23] via phase inversion
process. Chen et al. applied a 6-coat phase-inversion process
to produce a highly pore-oriented, ultra-thin ~220 mm anode
support tube. While this approach greatly facilitates mass
transport, as previously mentioned, the thin and anisotropic
nature of the support can potentially compromise robustness.
Further, the lengthy multi-step, multi-coat phase inversion
fabrication process may not be ammenable to volume
production.
Electrochemical Impedance Spectroscopy (EIS) analysis of
the baseline BCFZY-based cell under OCV mode (Fig. 4) reveals
significant decreases in both the ohmic resistance (measured
 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 2 e Cross-sectional microstructure of a tested cell. (a) and (b) low and high magnification images showing anode
support/electrolyte/cathode sandwiched structure after reduction and cell testing. (c) Exsolution of Ni particles in the
electrolyte phase on the anode side was observed. (d) The cathode (BCFZY, in this example) is porous and homogeneous
with <100 nm particle size.

Fig. 4 e Electrochemical Impedance Spectroscopy (EIS)

analysis of a tubular cell with BCFZY cathode at different
temperatures.

Fig. 3 e Polarization and power density curves of a single

tubular cell with BCFZY cathode at different temperatures.
via the high frequency intercept of the EIS spectrum) and
polarization resistance (measured by the width of the
impedance arc) as the temperature increases from 500 to
600  C. At 600  C, the cell performance is predominantly
limited by ohmic resistance. Further improvements should
therefore seek to decrease the total ohmic resistance, focusing
particularly on enhacing electronic conduction in cathode,
decreasing ionic resistance in the electrolyte layer (e.g. via a
thinner electrolyte), and mitigating contact and interfacial
resistance at the electrolyte/electrode interfaces (e.g. via
introduction of functional layers or interfacial contact layers).
We subsequently tested the performance of a BCFZY-based
2-cell tubular short stack using series cell connection (Fig. 5).
The two-tube bundle produces a 2.0 V OCV and reaches a total
maximum power of 2.3 W at 600  C. The lower average OCV
produced by the two-tube bundle (~1 V) as compared to the
individual single cells (~1.08 V) in Fig. 3 indicates possible
leakage in the stack assembly. The maximum power density
of the twodtube stack, normalized to the total electrode area,
reaches ~280 mW cm2. This is significantly lower than that of
the single cell (517 mW cm2), which we again attribute to
challenges with gas manifolding and cell sealing as well as a

Please cite this article as: Zhu L et al., High performance tubular protonic ceramic fuel cells via highly-scalable extrusion process,
International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.06.018
6 international journal of hydrogen energy xxx (xxxx) xxx

switch from a 4 probe measurement configuration for single-

tube testing to a 2 probe measurement for the two-tube
testing, which prevents elimination of the electrical wire
lead and contact resistances.

Comparison of BCFZY, BSCF and PBSCF cathodes

An important objective of this study is to compare recently-

Fig. 5 e IV and power characteristics of the 2-cell short
tubular stack with BCFZY cathode at 600  C.
reported high-performance PCFC cathodes (BCFZY [1], BSCF
[6], and PBSCF [3]). We utilize a single tubular cell ancestor to
provide a consistent and reliable comparison. Here we use the
stoichiometric cathode compositions exactly as reported by
these previous studies but otherwise use identical materials
synthesis processes, cathode application and testing proced-
ures to minimize any impact from experimental or processing
variations. Fig. 6 compares the XRD pattern of the three syn-
thesized cathode powders. All three powders are synthesized
by the same sol-gel approach and each show a similar

Fig. 6 e Comparison of the three cathode powders. (a) XRD patterns of the three synthesized cathode powders with a
reference comparison to the perovskite-type SOFC cathode La0.6 Sr0·4Co0·9Fe0·1O3-d (LSCF): pdf# 01-089-5720. For this XRD
comparision, the cathode powders were first further calcined at 900  C for 5 h to mimic the real conditions after cathode
application on cells. (b) A photograph taken under the same background exposure shows the PBSCF is the blackest, BCFZY is
less dark (approximately dark-brown). The color of the BSCF powder is between PBSCF and BCFZY, but closer to PBSCF. The
cathodes shown in the photograph were only calcined at 600  C. (For interpretation of the references to color in this figure
legend, the reader is referred to the Web version of this article.)

Please cite this article as: Zhu L et al., High performance tubular protonic ceramic fuel cells via highly-scalable extrusion process,
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 international journal of hydrogen energy xxx (xxxx) xxx 7

perovskite-type pattern (here referenced to La0.6 Sr0.4 Co0$9Fe0.1,

LSCF, pdf# 01-089-5720). Relative to the LSCF reference pattern,
the diffraction peaks of the three cathode materials increas-
ingly shift toward lower angles from PBSCF to BSCF to BCFZY,
reflecting the increasing lattice parameter. Although PBSCF has
been generally reported as a double perovskite and refined to
the orthorhombic structure (pmmm, space group# 59) [36,37],
the absence of doublets here and also as seen in other reported
double perovskite structure cathode materials such as Pr0.5-
Ba0$5CoO3-d (PCO) suggests that its structure may be highly
sensitive to the materials preparation method [38]. For direct
comparison, we firstly treated PBSCF also as cubic perovskite
(pm-3m, space group #221). Lattice refinement to cubic perov-
skite yields a lattice constant a of 3.881, 4.005, and 4.115
A for
PBSCF, BSCF and BCFZY, respectively. The refined cell param-
eters for both BSCF and BCFZY are close to those reported in the
literature [1,38]. It is worth mentioning that if the PBSCF is Fig. 7 e IV and power density performance comparison of
treated as double perovskite and refined to orthorhombic small, nominally identical tubular cells (all cut from a
structure instead, then a and b remain ~3.881
A while c becomes single parent tubular half-cell) with either BCFZY, PBSCF or
~2a, i.e., ~7.762

A. These values are close to those obtained by BSCF cathode at 600  C.
Jiang et al. (3.851, 3.854, and 7.715

A for a, b, and c, respectively)
by refining to the double perovskite structure [37]. These results
shows signs of activation polarization limitation (reflected in
also suggest that it is likely possible to synthesize many other
its concave shape) in the low to mid-range current density
similar cathode materials by moderate substation of the A site
region. The BSCF-based cell also shows slight hints of such
and B site elements with other metal elements in the cubic
effects, but the BCFZY-based cell produces a consistently
perovskite structure, leveraging identically the same synthesis
convex j-V curve shape and instead shows signs of possible
procedure used in this study.
mass transport limitations in the higher current density re-
Fig. 6b compares the visual color of the three cathodes.
gion which likely contribute to its slightly lower MPD.
After calcination, PBSCF and BSCF show a pure black color,
EIS analysis under OCV mode (Fig. 8) is consistent with the
similar to black charcoal. BCFZY, while still very dark, is not
observations extracted from the j-V curve measurement. The
pure black (note the color difference is not quite differentiable
BSCF-based cell has the lowest total cell area specific resis-
when captured by a camera as compared with observation by
tance (ASR) therefore achieving the highest MPD, while the
naked eye). It is known that the apparent color of materials
PBSCF-based cell has the highest ASR, leading to the lowest
like semiconductors can usually be explained by band gap,
MPD. Based on the low and high frequency intercepts, it is
free electron concentrations, surface smoothness, etc. [39]
clear that the PBSCF cell is largely limited by the electrode
The difference in the apparent color seen here may suggest
polarization resistance as measured by the size of the
slightly different intrinsic physical properties in these three
extended impedance arc, and reflecting the contributions
cathodes.
from both activation and mass transport effects. Due to the
Fig. 7 compares the cell performance under dry H2/
concave shape of the j-V curve, it may be further suggested
humidfied air at 600  C for the three cathodes. MPDs of 534,
that the activation polarization resistance dominates the
517, and 326 mW cm2 are obtained for BSCF, BCFZY, and
PBSCF, respectively. Although the three cells came from a
single tube and were fabricated and tested identically, they
show slightly varying OCVs. We attribute this phenomena to
slight leaks or sealing differences during cell assembly. Such
small leaks may cloud results. However, we note that the
material with the lowest OCV demonstrates the highest power
density, implying that gas leakage is not responsible for the
observed performance differences. It is not surprising that
BSCF shows the highest MPD performance among the three
cathodes, although it is generally considered as only having
mixed oxygen ion and electronic conduction and was origi-
nally developed for conventional SOFC applications. Indeed,
to our knowledge the highest performance ever reported for a
PCFC came from a planar cell that employed a BSCF cathode
[6]. On the other hand, the PBSCF cells shows noticeably lower
performance although it has also previously been reported to
produce high performance in PCFC button cells, albiet under
different synthesis and testing conditions than those used Fig. 8 e Comparision of EIS results of cells with BCFZY,
here [3]. Interestingly, the j-V curve for the PBSCF-based cell PBSCF and BSCF cathode at 600  C.

Please cite this article as: Zhu L et al., High performance tubular protonic ceramic fuel cells via highly-scalable extrusion process,
International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.06.018
8 international journal of hydrogen energy xxx (xxxx) xxx
behavior of the PBSCF-based cell. In contrast, the BCFZY-
based cell shows the lowest total polarization resistance
(smallest arc) but has a much larger ohmic resistance as seen
by its significantly higher high-frequency impedance inter-
cept than either the BCFZY or PBSCF cells. Thus, ohmic
resistance dominates the behavior of the BCFZY-based cell, in
agreement with its j-V curve and consistent with findings
from previous studies [1].
This study, based on controlled tests and parallel com-
parision from nominally identical tube segments, suggests
that the BCFZY-based cell may, in part, be limited by ohmic
conduction within the cathode itself. In other words, further
improvement could likely be obtained by considering doping
strategies to increase the electronic conductivity of BCFZY
and/or blending with a highly conductive second phase [40].
We hypothesize that the relatively lower electronic conduc-
tivity of BCFZY vs. BSCF and PBSCF is likely due to the
appreciable amount of Zr and Y doping which are introduced
to increase its oxygen ion and proton conduction [1,41,42]. We
note the inherent tradeoffs in cathode design, however, as
these large, fixed-valent cations also enhance the structural
and chemical stability of BCFZY (especially vs. BSCF), illus-
trating the potentially complex and multi-variate challenges
of cathode optimization.
Summary
We established an effective and facile method to fabricate
long green tubes for protonic ceramic cells (PCCs) that yields
good power density performance (>500 mW cm2) under H2/
air fuel cell testing. The process is well positioned for large-
scale PCC applications. We also used the tubular architec-
ture to evaluate three state-of-the-art high-performance PCFC
cathodes (BCFZY, BSCF, and PBSCF). Specific summary from
this study include:
1) Up to 66 cm long straight green anode supports can be
successfully extruded using the common NiO/BCZYYb
protonic ceramic materials set. Hang-firing leads to high
quality anode supported tubular PCFCs.
2) Using the BCFZY cathode, the maximum power density
reached 164, 308, and 517 mW cm2 at 500, 550, and 600  C,
respectively. A short 2-cell stack delivered 2.3 W power
output with a total active tube length of 3.2 cm and a
diameter of 0.82 cm at 600  C.
3) At 600  C, segments cut from a common parent tube coated
with BSCF, BCFZY, and PBSCF-based cathodes attained
maximum power densities of 534, 517, and 326 mw cm2,
respectively.
4) The BSCF-based cell showed the lowest ohmic resistance
and modest polarization resistance, leading to the lowest
overall total resistance and the highest MPD. The BCFZY-
based cell has the lowest total polarization resistance but
much larger ohmic resistance, leading to a slightly higher
total resistance and slightly lower MPD than BSCF. The
PBSCF-based cell has an ohmic resistance close to BSCF but
a total polarization resistance about twice that of the BSCF
cell and four times of the BCFZY cell which result in the
lowest performance and the lowest MPD.
Please cite this article as: Zhu L et al., High performance tubular protonic ceramic fuel cells via highly-scalable extrusion process,
International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.06.018
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
The information, data, and work presented herein was funded
in part by the Advanced Research Projects Agency-Energy
(ARPA-E), U.S. Department of Energy, under Award Number
DE-AR0000808 and by the Army Research Office under grant
number W911NF-17-1-0051. The views and opinions of au-
thors expressed herein do not necessarily state or reflect those
of the United States Government or any agency thereof.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2021.06.018.
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INDEX
 INDEX
Adams Presses, 50
Æthelwald, 122
Alba, the Duke of, 233
Alcuin Bible, the, described, 125–127
Alcuin, Bishop, of York, 125, 126
Aldine Press, the, at Venice, saved by intervention of Jean Grolier, 56, 238;
printing at, 206–215;
the Jenson office combined with, 214
Aldus Manutius, legend over office of, 10;
his confidence in permanence of the printed book, 11–12;
his type designs, 17;
establishes his office in Venice, 206;
his printer’s mark and slogan, 207, 208;
changes format of the book, 207;
his aims, 208;
the Greek classics of, 209;
his contributions to typography, 210;
his Hypnerotomachia Poliphili, 210–213;
Jean Grolier’s friendship with family of, 214–215
Allegro, l’, Milton’s, 93
Ambrosiana Iliad, the, 24, 25
Ambrosiana Library, the, humanistic manuscripts in, 24, 25
Angelico, Fra, 149, 290
Anglo-Saxon missionary artists, the, 125
Anne, of Brittany, Hours of, described, 149–151
Anne, Saint, 138
Antiquities of the Jews, the, described, 138–141, 146
Antonio del Cherico, Francesco d’, Book of Hours illuminated by, 111, 113,
116, 146–149, 290
Antwerp, the leading city in Europe, 223;
book manufacture in, 224;
under Spanish domination, 227;
loses her pre-eminence, 233;
purchases the Plantin office, 235;
referred to, 239
Apostrophes, Bernard Shaw’s ideas concerning, 68
Arnold, Matthew, 178
Ashburnham Collection, the, 148, 284
Augustinus, 202
Austria, the Emperor of, 105
Authors, relations between publishers and, 51, 63;
their attitude toward the physical format of their books, 67

Bandini, librarian of the Laurenziana Library, 284

Baptistery, the, at Florence, 273
Barbaro, Marco Antonio, Procurator of Saint Mark’s, 143
Bardi, the, 297
Bardi, Bardo, 297
Barlow, Sir Thomas, 85
Baskerville, John, his editions, 245;
letter from Benjamin Franklin to, 245;
his types, 245–246;
his Virgil, 246–250;
first to introduce glossy paper, 250;
Dibdin’s estimate of, 251;
referred to, 95, 244
Baynes, Ernest Harold, 104
Bedford, Anne, Duchess of, 135, 137
Bedford Book of Hours, the, described, 135–138, 146
Bedford, John, Duke of, 135, 137
Belgium, see Netherlands, the
Bellini, Giovanni, 213
Beowulf, William Morris’, 259
Berlin, library of, 196
Berry, the Duc de, the Très Riches Heures of, 116;
the Antiquities of the Jews begun for, 139
Bertieri, Raffaello, 32
Bewick, Thomas, 163, 251
Biagi, Dr. Guido, custodian of the Buonarroti and the da Vinci archives, 14,
182, 290;
defines the humanist, 15, 162;
his association with the designing of the Humanistic type, 17–33;
his comments on Bodoni, 78;
his meeting with Charles Eliot Norton, 180–183;
described, 277;
in the Laurenziana Library, 277–300;
his early ambition to become librarian of the Laurenziana, 284;
in America, 299;
his last days, 299–300;
his death, 300;
referred to, 14, 16, 17, 111
Bible, the, welfare of men and of empires based upon, 224
Biblia Amiatina, the, 287, 288
Biblia Polyglotta, Plantin’s, 227;
the story of, 227–233;
pages from, 229–231
Bibliothèque Nationale, the, Paris, 119, 127, 128, 139, 140, 141, 149, 196,
198, 220
Billfrith, Saint, 122
Bindings, 113, 288
Birmingham, England, 244
Biscioni, librarian of the Laurenziana Library, 283
Bisticci, quoted, 12
Blanche, Queen, of Castile, 129
Boccaccio, 287
Bodleian Library, the, 196
Bodoni, Giambattista, the father of modern type design, 78–82, 251;
compared with Didot, 252, 257;
referred to, 95
Bodoni Press, the revived, in Montagnola di Lugano, 79
Bodoni type, the, 78;
compared with the Didot type, 79–82;
William Morris’ dislike of, 80;
De Vinne’s admiration for, 80, 82;
estimate of, 257
Bokhara, 118
Bomberghe, Corneille, type designer, 228
Book, the, conception of early patrons of, 11;
lure of, 37;
the tangible expression of man’s intellect, 112.
See also, Illuminated book, Printed book, Written book
Bookmaking, in 1891, 42–54;
the weakness of method in, 54
Book of Hours, by Francesco d’Antonio del Cherico, 111;
described, 146–149;
referred to, 290
Books, cost of making, 58
Bookselling, inadequate methods in, 60
Boston, Howell’s comments on, 186
Boston Society of Printers, the, 99
Bourbon, Pierre II, Duc de, 140
Bourdichon, Jean, 113, 149, 150
Boyd, Henry, 26, 27
Brays, the, 292
British Museum, the, 27, 28, 117, 119, 122, 125, 132, 135, 166, 196, 298, 299
Broad Chalke, England, Maurice Hewlett’s home at, 157
Browne, Sir Thomas, 207
Budé, Guillaume, 214
Buonarroti, see Michelangelo
Buonarroti archives, the, 14, 182, 290
Burne-Jones, Sir Edward, and the Kelmscott Chaucer, 259, 261, 262;
referred to, 6
Burney, Fanny, 163
Byron, Lord, manuscript of his letters burned by John Murray III, 65
Byzantine illumination, see Illumination, Byzantine
Byzantine ink, 112

“Cabin,” the, Howell’s, 186

Cable, George W., 177
Cæsar, Elzevir’s, 240
Cambridge Immortals, the, 178
Camp, Walter, 84
Campanile, Giotto’s, at Florence, 273
Campanile, the, at Venice, 145
Carlyle, Thomas, 178
Carnegie, Andrew, 174–177
Carnegie, Mrs. Andrew, 174
Caroline minuscule, the, 126
Carolingian illumination, see Illumination, Carolingian
Carolingian School, the, in France, 125
Caslon foundry, the, 245, 246
Castiglioncello, Italy, 162
Cato, quoted, 208
Caxton, William, work of, compared with Jenson’s, 244
Cellini, Benvenuto, autobiography of, 287
Celtic illumination, see Illumination, Celtic
Censors, the, 221
Ceolfrid, Abbot of Wearmouth, 288
Ceriani, Monsignor, librarian of the Ambrosiana Library at Milan, described,
24;
his work on the Ambrosiana Iliad, 24, 25;
quoted, 25
Chantilly, the Musée Condé at, 116
Charlemagne, Emperor, 125
Charles, King, of France, son of King John, 129
Charles, King, of France, son of King Charles, 129
Charles V, emperor of the Holy Roman Empire, 216, 276
Charles VIII, of France, 282
Chaucer, the Kelmscott, the story of, 259–268
Chaucer type, the, designed by William Morris, 20
Chianti Hills, the, 171
Chiari, 297
Chinese, the, 7
Cicero, the Medicean, 283
Cicogna, Doge Pasquale, 143
Cimabue, Giovanni, 147
Clemens, Clara, 172, 174
Clemens, Samuel L., see Twain, Mark
Clemens, Mrs. Samuel L., 172, 173
Clement VII, Pope, 214, 276
Clovio, Giulio, 149, 290
Cobden-Sanderson, T. J., quoted, 96, 97;
estimate of, 96–101;
described, 98;
in Boston, 98–99;
importance of his work, 263;
his Ideal Book
quoted, 264;
his Doves Bible, 264–268;
referred to, 3, 68, 71, 95
Cockerell, Douglas, 262
Codex Argenteus, the, 119
Cole, Timothy, 106
Colonna, Francesco, 210
Colvin, Sir Sidney, 27, 28
Constable, Archibald, publisher, 66
Constantinople, might have become center of learning of XV century, 8;
destroyed by fire, 117;
the rebirth of, 118
Cosimo il Vecchio, and the Laurenziana Library, 280;
his personality and history, 280–281;
his fame as a chemist, 284
Cosimo II, and the Laurenziana Library, 283
Costs of making books, in 1891, compared with present costs, 48
Costume Antico e Moderno, Ferrario’s, 296
Country Printer, the, Howell’s, 187
Crasso, Leonardo, 210
Cremona, early printing at, 286
Curtis, George William, 178
Cuthbert, Saint, 120, 121, 122
Cyrus, King, 139

Danes, the, 120

Dante, proposed edition in Humanistic type of, 19, 32;
referred to, 158, 182;
Biagi’s work on, 182, 299;
the haunts of, 291
“Dawn and Twilight,” Michelangelo’s, 275
“Day and Night,” Michelangelo’s, 275
De Asse, Budé’s, 214
De Bure, discoverer of the Gutenberg Bible, 198
Decameron, the, manuscript copy of, 287
De Civitate Dei, Augustinus’, 202
Decorations, 116
Del Furia, librarian of the Laurenziana Library, 284
Delmonico’s, in New York City, 176
Deput, quoted on the innovations of the Elzevirs, 240
De Veritate Catholicæ Fidei, 93
De Vinne Press, the, New York, 42
De Vinne, Theodore L., 6;
his admiration for the Bodoni type, 80, 82
Dibdin, quoted on Baskerville, 251;
on Antonio Magliabecchi, 295
Didot, Firmin, the father of modern type design, 78–82;
his type discussed, 79–82, 257;
referred to, 39, 95, 257
Didot, Pierre, his Racine, 252–258
Didot Press, the, Benjamin Franklin at, 252
Didot type, the, compared with the Bodoni type, 79–82
Didots, the, in Paris, 251;
 compared with Bodoni, 252
Dobson, Austin, 158, 162–169;
his lines on Richard Garnett, 166, 167;
his ideas on fiction, 168;
his methods of work, 169;
his handwriting, 169
Dobson, Mrs. Austin, 168
Doves Bible, Cobden-Sanderson’s, described, 264–268
Doves Press, the, in London, 3, 70, 96, 263
Doves type, the, designed by Emery Walker, 18, 19;
specimen page of, 23;
in the Doves Bible, 264–268
Duneka, Frederick, 184
Dürer, Albrecht, 95
Dyck, Christoffel van, 243

Eadfrith, Bishop, 122

Earthwork Out of Tuscany, Hewlett’s, 159, 162
Eddy, Mrs. Mary Baker, 52–54
Edward VII, King, of England, 85, 140, 141
Egyptians, the, 118
Elchi, Count Angiolo Maria d’, 285
Eliot, George, in the Magliabecchian Library, 291–298;
her diary quoted, 296;
volumes consulted in writing Romola, 296–298
Elzevir, Abraham, editions of, 240;
his Terence, 241–243
Elzevir, Bonaventura, editions of, 240;
his Terence, 241–243
Elzevir, Isaac, becomes printer to the University of Leyden, 240
Elzevir, Louis, founder of the House of Elzevir, 239, 240
Elzevir, the House of, craftsmen rather than artists, 238;
in Leyden, 240;
adopt new format for the book, 240;
their editions, 240–243;
their types, 243;
their business organization, 243;
estimate of importance of their work, 243;
referred to, 95, 237, 251
England, typographical supremacy of, 194, 244–250;
second supremacy of, 258–268
English illumination, see Illumination, English
Engravings, steel, 105
Epistolæ ad Familiares, Cicero’s, 285
Ethics, in business, 65
Étienne, Henri, ruined by his Thesaurus, 56, 238;
in Geneva, 223
Étienne, Robert, becomes “printer in Greek” to François I of France, 216;
the Royal Greeks of, 219–222;
leaves France, 223;
death of, 223;
his Roman type, 222;
referred to, 252
Eugenius, Pope, 281
Evreux, Queen Jeanne d’, 129
Explicit, the, 92;
examples of, 94, 202, 204, 206, 285
Ezra, the Prophet, portrait of, 288

Famiglie del Litta, Le, 297

Felton, Cornelius Conway, President of Harvard University, 50
Ferrara, early printing at, 286
Ferrari, Dr. Luigi, librarian of the San Marco Library, Venice, 145
Ferrario, 296
Field, Eugene, described, 38;
manuscript of, 39, 41;
referred to, 38, 55
Fielding, Henry, 163
Fiesole, the heights of, 298
Firenze Antica e Moderna, Rastrelli’s, 297
Firenze Illustrata, Migliore’s, 296
Fiske, Willard, 26, 27
Flemish illumination, see Illumination, Flemish
Fletcher, Horace, friend of Eugene Field, 41;
philosophy of, 75, 82, 84;
his ideas of typography, 75;
page of his manuscript, 77;
his dinner at Graduates’ Club, New Haven, 84;
importance of his work, 85;
his friendship with William James and Henry James, 86;
letter from Henry James to, 87;
visit to Lamb House, 89
Fletcherism, 75, 83
Florence, Italy, the most fascinating city in Europe, 273;
early printing at, 286
Florence, the Grand Duke of, 295
Forest Lovers, the, Hewlett’s, 157, 158
Foucquet, Jean, 113, 138, 140, 149
France, typographical supremacy of, 194, 215–223;
loses supremacy, 223;
second supremacy of, 251–258
François I, of France, becomes patron of learning and culture, 216;
makes Robert Étienne “printer in Greek to the King,” 216;
his interest in printing, 216–221;
his relations with the censors, 221;
 referred to, 214, 216
Frankfort, 227
Franklin, Benjamin, quoted on the Baskerville editions, 245;
his letter to Baskerville, 245;
at the Didot Press, 252
French illumination, see Illumination, French
French Republic, the, 141
French School of Painting, the, 139
Fust, John, 198, 199

Gabrilowitch, Mrs. Ossip, 172

Garamond, Claude, 220
Garnett, Dr. Richard, 164, 165;
lines written by Dobson on, 166, 167;
estimate of, 166
General Theological School Library, the, New York, 196
Genesis, the Cottonian, 117
Geneva, the Étiennes at, 223
George, Saint, 137
Germany, not sufficiently developed as nation to take advantage of
Gutenberg’s discovery, 8, 9;
brief typographical supremacy of, 194–201;
loses supremacy, 201
Gherado, 149, 290
Gilder, Richard Watson, 177
Giotto, 147, 273
Golden Gospels of Saint Médard, the, described, 127–128
Golden type, the, designed by William Morris, 18
Gold leaf, 116
Gold, Oriental, 112
Goldsmith, Oliver, 163
Gothic illumination, see Illumination, Gothic
Gozzoli, Benozzo, 149, 290
Graduates’ Club, the, in New Haven, 84
Grandjon, Robert, 228
Greece, the rich humanities of, 15
Greek classics, the, first printed by Aldus, 209
Greeks, the, 7
Greek types, 56, 219–221, 238
Grimani Breviary, the, described, 141–145, 146, 149
Grimani, Cardinal Domenico, 142, 143
Grimani, Doge Antonio, 143
Grimani, Giovanni, Patriarch of Aquileia, 142
Grimani, Marino, Patriarch of Aquileia, 142
Grolier Club of New York, the, 213
Grolier, Jean, saves the Aldine Press by his intervention, 56, 238;
his friendship with family of Aldus, 214–215;
his letter to Francesco Torresani, 215
Guidobaldo, Duke of Urbino, 210
Gutenberg Bible, the, described, 194–201;
rubricator’s notes, 196, 197
Gutenberg, John; the Bible printed by, 194–201;
referred to, 7, 194, 198, 234, 237

Hadley, Pres. Arthur T., 84

Halftones, 105–107
Hammond, John Hays, 84
Hand lettering, the art of, 10.
See also, Humanistic hand lettering, Semi-uncial characters, Minuscule characters
Harkness, Mrs. Edward S., 196
Harper and Brothers, 90, 183, 184
Harper’s Magazine, 183
Harte, Bret, 184
Harvard College Library, the, 245
Harvard University, Cobden-Sanderson’s lectures at, 99
Harvey, Col. George, gives birthday dinner to Mark Twain, 176;
gives birthday dinner to William Dean Howells, 187
Hautin, 228
Hay, John, 184
Hay, Mrs. John, 184
Heidelberg, 227
Heimskringla, the, William Morris’ translation of, 260
Heinsius, letter from Deput to, 240
Henri II, of France, 136, 221
Henry IV, of England, 135
Henry VI, of England, 136
Henry VIII, of England, 216
Hewlett, Maurice, 155–162;
describes the cloister of San Lorenzo, Florence, 275
Hoar, Senator George F., makes attack on Charles Eliot Norton, 179
Hogarth, William, 163
Holbein, Hans, 95
Holland, the natural successor to Belgium in supremacy of printing, 239.
See also Netherlands, the
Holmes, Oliver Wendell, 178
Homer, the Ambrosiana, see Iliad, the Ambrosiana
Hoover, Herbert, 85
Houghton, Henry O., 6
Hours of Anne of Brittany, the, 146;
described, 149–151
Howells, William Dean, 177;
recollections and reflections on, 183–188;
the Harvey birthday dinner, 188
Humanism, Petrarch the father of, 15
Humanist, the, defined, 15, 160–162
Humanistic hand lettering, 16, 21, 24, 126
Humanistic manuscripts, the, in the Laurenziana Library, 16, 21;
in the Ambrosiana Library, 24
Humanistic movement, the, far-reaching influence of, 15;
the forerunner and essence of the Renaissance, 15;
significance of, 16, 160
Humanistic scribes, the, see Scribes, the humanistic
Humanistic type, the, first idea of design of, 17;
proposed edition of Dante in, 19, 32;
work upon, 19–24, 126, 159, 180, 181
Huntington, Henry E., library of, 196
Hypnerotomachia Poliphili, the, printed by Aldus, 210;
described, 210–213

Ideal Book, The, Cobden-Sanderson’s, 3, 99;

quoted, 264
Iliad, the Ambrosiana, 24, 25, 117
Illuminated book, the, attitude of Italian patrons toward, 11–12
Illumination, the art of, encouraged by Italian patrons in XV century, 11–13;
the underlying thought in, 112;
rich rewards in study of, 114;
various schools of, 114;
means of identifying various schools and periods, 115;
manuscripts which mark the evolution of, 116–119;
the Celtic School, 119–125;
 the Carolingian School, 125–128;
the Gothic School, 128–131;
the English School, 131–134;
the French School, 135–141, 149–151;
the Flemish School, 141–145;
the Italian School, 146–149;
cause for the decline of, 151;
opportunities for studying, 152
Illumination, Byzantine, described, 118;
referred to, 124, 125, 127
Illumination, Carolingian, 125–128
Illumination, Celtic, 119–125, 126, 129
Illumination, English, 114, 131–134
Illumination, Flemish, 114, 137, 139, 141–145, 149, 150
Illumination, French, 114, 135–141
Illumination, Gothic, 114, 128–131
Illumination, Italian Renaissance, 114, 146–149, 150
Illumination, Romanesque, 114
Illustration, 105
Imperial Library, the, in Vienna, 117
Incipit, the, 93
India, 112, 118
Ink, Byzantine gold, 112, 118;
inferior quality introduced, 238;
Didot’s, 258
Innocents Abroad, Mark Twain’s, 170
Ireland, 121
Irish monks, the, see Monks, the Irish
Irish School of Writing and Painting, the, 120
Italian illumination, see Illumination, Italian
Italic type, first used by Aldus, 17, 286;
said to be based on handwriting of Petrarch, 17, 210;
Baskerville’s, 245;
Didot’s, 257
Italy, life and customs of people of, in XV century, 8;
illumination slow in getting a hold in, 146;
typographical supremacy of, 194, 201–215;
loses supremacy, 215;
culture in the XVI century in, 223

James, Henry, Horace Fletcher’s friendship with, 86;

quoted, 86;
estimate of, 86;
letter to Horace Fletcher from, 87;
quoted, 88
James, William, Horace Fletcher’s friendship with, 86;
quoted, 86;
letter from Henry James to, 88;
his interest in printing, 90, 92
Jenson, Nicolas, type designs of, 18, 19, 22, 202, 205, 206;
the explicit in books printed by, 94, 202;
printer’s mark of, 203, 207;
sent to Germany by Charles VII of France, 204;
establishes his office in Venice, 204;
death of, 206;
his office combined with the Aldine Press, 214;
Caxton’s work compared with, 244;
referred to, 216, 286
Jenson’s Gothic type, 202, 205, 206
Jenson Roman type, the, 18, 19, 206, 268;
sample page of, 22
Joan of Arc, Mark Twain’s, 170
John of Spires, 285
Jones, George W., 32
Joseph, Saint, 138
Josephus, Flavius, 139
Justinian, the Emperor, 117
Justinian, the Pandects of, 287

Keats, John, 158

Keere, Van der, 228
Kelmscott Chaucer, the, see Chaucer, the Kelmscott
Kelmscott Press, the, 6, 55, 70, 96, 259–268
Kelmscott volumes, the, 259–268;
estimate of, 263
Koreans, the, 7

Labels, paper, 92
Lamb House, Rye, Henry James’ home, 89
Lapis lazuli, used in printing ink, 30;
in illumination, 118
Laura, see Sale, Madonna Laura de Noves de
Laurenziana Library, the, humanistic volumes at, 16;
illuminated volumes at, 119, 148, 287;
uninviting approach to, 273;
the Sala di Michelangiolo, 276;
Dr. Guido Biagi at, 277–300;
the great staircase, 278;
Vasari’s work in, 278;
the story of, 280–284;
the treasures of, 284–289;
the Hall of Tapestries, 285;
the Tribuna, 285;
the printed books in, 285;
the spell of, 300;
referred to, 14, 21, 94, 111, 182
Le Bé, Guillaume, 228
Lee, Sir Sidney, 86, 174, 175
Leigh, Maj. Frederick T., 184
Leipzig, library of, 196
Lelio, Lucrezia, 213
Leo X, Pope, 282.
See also Medici, Giovanni de’
Lettering, see Hand lettering
Letters, raised gold, 116
Lewes, George Henry, in the Magliabecchian Library, 292–298
Leyden, heroic resistance to Spanish siege, 239;
becomes the intellectual and literary center of Europe, 239;
Plantin in, 239;
the Elzevirs in, 239–240
Leyden, the University of, 239;
Plantin made printer to, 239;
Isaac Elzevir made printer to, 240
Lindisfarne Gospels, the, described, 119–125
Lippi, 296
Lippi, Fra Filippo, 28
Lipsius, the historian, 239
Lithography, 105
Little Novels of Italy, Hewlett’s, 159
Lockhart, John Gibson, 66
Longfellow, Henry Wadsworth, 178
Longmans, London publishers, 66
Lorenzo the Magnificent, see Medici, Lorenzo de’
Lorraine, the House of, and the Laurenziana Library, 283
Louis XI, of France, 140
Louis XII, of France, 150
Louis XIV, of France, 198