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Journal of Energy Storage 99 (2024) 113329
Contents lists available at ScienceDirect
Journal of Energy Storage

journal homepage: www.elsevier.com/locate/est
Research papers
Cobalt-free cathodes and silicon thin-film anodes towards high-capacity

solid-state batteries
Ryan Brow a, * , Zachary Berquist b, c , Steven Lee d , Trevor Martin b, c , Lydia Meyer a ,
Maxwell Schulze a , Avtar Singh a , Ryan Tancin c , Glenn Teeter c , Gabriel Veith e , Bertrand
J. Tremolet de Villers c , Andrew Colclasure a, * , Arumugam Manthiram d, *
a
Center for Integrated Mobility Sciences, National Renewable Energy Laboratory, Golden, CO 80401, USA
b
Chemistry and Nanoscience Center, National Renewable Energy Laboratory, Golden, CO 80401, USA
c
Materials Science Center, National Renewable Energy Laboratory, Golden, CO 80401, USA
d
Science and Engineering Program and Texas Materials Institute at University of Texas at Austin Austin, TX 78712, USA
e
Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
A R T I C L E I N F O A B S T R A C T
Keywords: This study provides a comprehensive analysis of a novel battery system, which integrates a high-loading (~5
All-solid-state battery mAh/cm2) cobalt-free cathode composed of lithium nickel manganese aluminum oxide (LiNi0.9Mn0.05Al0.05O2,
No‑cobalt cathode NMA) into an all-solid-state cell for the first time. The argyrodite (Li6PS5Cl) solid electrolyte is used in
Nickel-rich cathode
conjunction with a 99 wt% silicon thin-film anode. Room temperature discharge capacities of >210 mAh/gNMA
Pure silicon anode
Argyrodite
and > 170 mAh/gNMA were achieved at cycling rates of 0.05C and 0.25C, respectively. Electrochemical
Pressure impedance spectroscopy measurements, taken during the first cycle detail onset of electrolyte degradation,
lithiation of the silicon anode, and the change in charge transfer kinetics as a function of cell voltage. Raman,
Fourier Transform Infrared, and X-ray photoelectron spectroscopy are used to identify the argyrodite degradation
products that form in the catholyte on cycling, unveiling lithium carbonate as a potential source of oxygen-
related degradation commonly alluded to in literature. Furthermore, high cell stack pressure, 350 MPa during
fabrication, led to fracturing and pulverization of some cathode particles.
1. Introduction and a less-reactive silicon anode.

The shift towards low-cobalt, nickel-rich transition metal layered
In the quest to increase the energy density of electrochemical energy oxides in cathodes is driven by their superior energy density and lower
storage devices, all-solid-state batteries (ASSBs) are emerging as a po- cost than their cobalt-rich counterparts. These materials, however,
tential contender [1]. Of the solid electrolyte materials, the argyrodite grapple with problems like cathode-electrolyte interface instability and
family of sulfur-based electrolytes (Li6PS5X where X = Cl, Br, or I) is one lack of consistent mechanical contact between the cathode and elec-
of the front runners in development. Argyrodite ASSBs offer a promising trolyte particles when cycled in solid-state cells [6]. Inconsistent me-
avenue towards higher energy density and longer lifespans [2]. How- chanical contact can partially explain the large range in reported
ever, the highest energy density ASSB architectures often employ cobalt cathode utilization in solid-state cell values across the literature [7–9].
containing cathode materials, which impedes the likelihood of their The cathode utilization can decrease further on cycling during which
widespread use due to elemental scarcity and supply chain constraints nickel-rich cathode materials experience a “c-axis collapse” above 4.2 V
[3,4]. Moreover, cell architectures with high energies often employ (all voltages are versus lithium metal unless stated otherwise) [10].
lithium metal anodes which cause instability when coupled with the Furthermore, cathode cracking can occur when using the energy-dense
argyrodite solid electrolytes that have a relatively small electrochemical nickel-rich cathodes, which can electrically and ionically isolate the
stability windows [5]. Herein, we report a new ASSB cell configuration now detached particles. While pre-cracking and coating these nickel-
that addresses both limitations by using a no‑cobalt cathode material rich cathodes has shown some promise in limiting particle isolation in
* Corresponding authors.
E-mail address: Ryan.Brow@nrel.gov (R. Brow).
https://doi.org/10.1016/j.est.2024.113329
Received 9 May 2024; Received in revised form 5 August 2024; Accepted 10 August 2024
Available online 17 August 2024
2352-152X/© 2024 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
R. Brow et al. Journal of Energy Storage 99 (2024) 113329
liquid cells, this method has yet to be explored thoroughly in solid-state fabrication (>350 MPa) and cycling pressures (>10 MPa) are often
cells [10]. This study is the first to use cobalt-free, LiNi0.9Mn0.05Al0.05O2 used to maintain intimate contact.
(NMA) cathode, which demonstrates excellent specific capacity (230
mAh/g) and high cycle-life retention in liquid-electrolyte-based cells, in • Stability window – As discussed above, the argyrodite electrolytes
a ASSB [11]. suffer from a narrow electrochemical stability window (~1.07–2.01
Lithium metal, despite its high energy density, faces challenges like V) [21]. This creates highly resistive electrolyte decomposition in-
dendrite growth and aggressive electrolyte reduction when used in terphases with both the cathode and anode. Below 1.7 V, the
solid-state batteries [12]. Due to the difficulty in using lithium metal argyrodite material forms P, Li2S and LiCl. Predictions made via
anodes, silicon anodes have gained great interest because of their high Density-functional theory (DFT) suggest that P is further reduced to
theoretical capacity, nearly ten times that of traditional graphite anodes form Li3P down to 0.8 V. This is set to occur via the decomposition of
[13]. The lithium alloying potentials with silicon are in the range of a the lithiated Li11PS5Cl phase which, has very low activation energy
few hundred mV above lithium plating potentials, meaning the issue of for decomposition [22]. This interphase at the anode can have ionic
lithium dendrites causing internal short circuiting through the solid- conductivities as low as 3.2 × 10− 6 S cm− 1 [23] and can be 10–250
state electrolyte separator can potentially be avoided. Silicon’s high nm thick, depending on the method used to measure it [24,25].
lithiation capacity theoretically also allows high energy densities close The oxidation products of the argyrodite LPSC at the cathode
to those achievable only with lithium metal anodes, a performance interface are thought to be Li3PS4, S and LiCl, where Li3PS4 can be
metric that other intercalation style anodes such as graphite will always further oxidized above 2.4 V to form P2S5 and then to P2S4− 7 above
fall short of. Silicon anodes have also demonstrated improved electro- 2.9 V [26]. However, there is some debate about whether LPSC un-
chemical stability against the sulfide-based argyrodite solid electrolytes dergoes direct decomposition or an indirect decomposition via the
and are not prone to dendrite formation, thereby circumventing the delithiated Li4PS5Cl phase. Somewhat interestingly, some studies
lithium metal interfacial instability issues that have been reported pre- report sulfate or sulfite species near the cathode-LSPC interface, and
viously [12]. The main obstacle with silicon is its significant volume others do not [27]. This will be discussed in greater detail below.
expansion during lithiation, which can lead to mechanical degradation There is some evidence to suggest that there can be polysulfides
and reduced silicon-electrolyte contact [14]. However, the high stack formed via polymerization of the anions, which can form P–[S]n–P-
pressures typical of solid-state batteries may help overcome the volu- type anions species [28]. Additional decomposition products
metric changes of silicon anodes by maintaining silicon-electrolyte involving the cathode’s transition metals (transition-metal sulfides,
contact [15]. Meng et al. have demonstrated phenomenal performance phosphides, and chlorides) have been detected using ToF-SIMS;
of a 99 wt% micron-sized silicon anode which greatly limited anode/ however, they are assumed to play an insignificant role in capacity
electrolyte contact area [16]. This cell design allows for the use of high fade or increased cell resistance [28].
loading anode electrodes without the need for composites. While the use
of silicon anodes can eliminate the electrolyte’s exposure to the reducing • Dendrite formation – Two types of dendrite-like formations have been
potential of lithium metal, it is still an electronically conductive surface identified, soft and hard shorts. Hard shorts occur when there is a
at potentials below argyrodite’s stability window. complete electronic path between electrodes which, in ASSBs, is
Deiseroth et al. are typically credited with first proposing lithium-ion thought to usually occur via a lithium dendrite. These shorts are
substitution into the Ag8GeS6 argyrodite structure, yielding Li-ion typically easy to identify since they often cause a dramatic decrease
electrolytes with conductivities close to their liquid counterparts, in in the overall cell potential, causing the cell to behave more as a
the range of 10− 2 to 10− 3 S cm− 1 [17]. Argyrodites electrolytes Li6PS5X resistor [29]. Unfortunately, soft shorts are more difficult to recog-
(X = Cl, Br, I) have a face-centered cubic F43m symmetry in which the nize. Soft shorts describe a phenomenon where a moss-like, sub-
sulfur and halide anions form the cubic lattice while the PS3− 4 tetrahedra micron growth of lithium dendrites forms in the SSE layer. They are
occupy the octahedral sites. The room temperature transference number difficult to recognize because cells experiencing them often do not
is close to 1, and the ionic conductivity of crystalline Li6PS5Cl (LPSC) is lose their overall cell potential as the structures are too fine to pass
1.9 × 10− 3 S cm− 1 [18]. Argyrodites possess greater ductility than many high currents. It is thought that this sea of fine dendrites experiences
of the oxide-based solid electrolytes, allowing for better particle-particle electromigration (or perhaps thermal cutoff) on contact with the
contact in the cell. However, these systems still suffer from less-than- terminal electrode, disrupting the direct electron path [30]. This
ideal lithium transport, require high fabrication pressures, and have mechanism makes identifying soft shorts in full cells challenging and
narrow electrochemical stability windows [5]. has possibly led to the publication of data from cells that contain
Although the argyrodite materials contain great promise, three pri- them, unbeknownst to the authors [31].
mary challenges standout: an inability to maintain cathode-electrolyte
contact on cycling, a small electrochemical stability window, and Several factors seem to control for the prevalence of dendritic
dendrite formation (the latter two mechanisms may be related in some growth, including the Young’s modulus of the SSE [32], the size and
cases). orientation of grain boundaries [33], electrolyte degradation that is
conducive to lithium metal deposition, current density [34], tempera-
• Mechanical contact – All solid electrolytes encounter the issue of ture, and external pressure applied to the cell [35]. Phase field simula-
maintaining solid-solid contact with cathode and anode particles. tions were used to understand the relationship between continuous soft
This can be viewed from the perspective of a mismatch of mechanical shorts in SSEs and external pressure. These studies suggest that cells
properties such as Young’s modulus and hardness (the sulfide’s under higher external pressure were more likely to form dead lithium,
Young’s modulus and hardness are 20 GPa and 2 GPa where a typical dendrites that are no longer connected to either electrode [30].
transition metal oxide cathode’s are approximately 100 and 20 GPa The transition from lab-scale prototypes to commercial-scale pro-
respectively) [19]. An additional issue is the solid-state electrolyte’s duction of solid-state batteries is laden with challenges. Key areas of
inability to deform properly to accommodate the volume changes in focus include developing cost-effective, scalable manufacturing pro-
cathode active materials on cycling. These values can be as high 7 % cesses that can maintain low defect density, great active material-SSE
for LFP and single crystalline nickel-rich cathodes at top-of-charge particle contact at low pressure, and low overall cell resistance both
[19]. This can lead to a dramatic reduction in the cathode- pre and post-cycling. Moreover, the pressures required to accomplish
electrolyte contact. Consequently, there is a hefty increase in over- reasonable cell capacities at the lab scale (often >10 MPa) are unac-
all cell resistance (~130 Ω⋅cm− 2) [20]. To alleviate this issue, large ceptable at the commercial scale. These high pressures require bulky cell
enclosures and may induce cathode fracturing at high enough pressures.
2
Efforts and methods must be pursued to minimize the overall fabrication intimate mixing. The anode consisted of 99 wt% nano‑silicon (Oak
pressure used to consolidate cell stacks. Ridge National Laboratory; 230 nm diameter) [41] and 1 wt% PVDF
The three main issues facing solid-state cells can be influenced (Solvay 5130) thin film. Xylene (Sigma-Aldrich) was added to silicon/
greatly by the manufacturing process used. In addition, large scale PVDF mixture to form a slurry which was subsequently doctor-blade
manufacturing involves processes that can complicate the already coated onto a copper-foil current collector (12 μm thick) at a speed of
difficult to fabricate lab-scale prototypes (pellet cells) including the in- ~5 cm/s and a wet gap of 50 μm. These films were then dried in vacuum
clusion of binders [36], solvents [37], and wet or dry film deposition at room temperature overnight.
[38]. For LPSC, this must all take place in a dry room environment since Cells were assembled and cycled in a custom pellet press (12 mm
it readily hydrolyzes to form toxic H2S in air [39]. Additionally, since inner diameter) with titanium plungers and a polyether ether ketone
oxygen contamination in the electrolyte provides an additional (PEEK) body which is described in detail by Martin et al. [42] The silicon
decomposition pathway towards sulfate and sulfites, best practice may anode (5.55 mAh/cm2 with 1C = 1500 mAh/gSi) was added to the pellet
be to perform all of the LPSC processing in an inert environment [40]. press followed by ~100 mg of dry powdered LPSC which was subse-
We report, for the first time, an NMA–silicon hybrid cell that has high quently pressed at 300 MPa to form an approximately 300 μm thick
utilization, high loading, low impedance, and reasonable capacity separator layer. Next, the dry powdered catholyte (56 mg or 4.9 mAh/
retention. Specifically, this work demonstrates a novel ASSB cell cm2 with 1C = 180 mAh/gNMA) was then added on top of the SSE layer,
configuration that addresses lithium metal anode instabilities by utiliz- pressed to 350 MPa and then slowly released to the ultimate cycling
ing a silicon anode and that avoids cobalt scarcity issues by incorpo- pressure of 180 MPa. Formation occurred at C/20 (1C = 180 mAh/g)
rating a cobalt-free cathode material. Furthermore, we discuss the charge/discharge rates between 2.9 and 4.2 V. Subsequent charge and
degradation mechanisms of this cell architecture in detail using a variety discharge steps were all performed under constant current conditions at
of spectroscopic techniques which to our knowledge have not been re- approximately C/20 or C/4, between 2.9 and 4.3 V, followed by 1-h
ported previously for a no-cobalt NMC-type cathode chemistry. This was constant-voltage holds. Cells rested for 15 min between charge and
accomplished by using an extended mixing regimen of the various discharge. All cells were cycled at room temperature.
catholyte components (55 wt% NMA, LPSC argyrodite 44 wt%, Coin cells (CR 2032) were fabricated for EIS measurements. The
conductive carbon 1 wt%) and continuous pressure between the fabri- anode consisted to the same thin-film silicon described above. The
cation and electrochemical cycling steps. The anode is an impressive 99 separator was fabricated by first making a slurry of LPSC in xylene and
wt% thin-film silicon anode with 1 wt% binder. Several characterization doctor blade coating (200 μm wetgap) at ~5 cm/s onto a mylar film.
techniques suggest that the nickel-rich NMA does not experience addi- After drying, the film was pressed onto a porous polyaramid fabric (ACP
tional cathode-electrolyte degradation processes compared to those Composites) at 400 MPa to form a ~ 100 μm thick, free-standing sepa-
found in other nickel-rich NMC-type cathodes and lithium carbonate in rator [43]. The catholyte was made by adding 3 % by mass of poly-
the catholyte may be the source of oxygen-related phosphate and sulfate isobutene binder (in a xylene solution) to the NMA, LPSC, and VGCF
formation. mixture (50 wt% NMA, 45 wt% LPSC, 4 wt% Oppanol, 1 wt% VGCF).
Additional xylene was added to form a slurry which was doctor blade
2. Methods and materials coated onto Al foil using a doctor-blade coater with wet gap of 200 μm.
The final dry coating thickness was not measured. The 1st charge and
2.1. NMA synthesis discharge formation cycle were performed at a C/20 rate between 2.9
and 4.2 V with EIS interruptions every 30 min. Frequencies were swept
Cells constructed and tested in this manuscript utilized LiNi0.9M- in potentiostatic mode from 1 MHz to 10 mHz with an AC amplitude to
n0.05Al0.05O2 (NMA) as the cathode active material. NMA was synthe- 10 mA.
sized in the following procedure: First, the spherical
Ni0.9Mn0.05Al0.05(OH)2 precursor with a diameter of 10–12 μm was 2.3. X-ray diffraction
synthesized via coprecipitation as described in a previous publication
[11]. Aqueous solutions of NiSO4⋅6H2O, MnSO4⋅H2O, and Al X-ray diffraction (XRD) measurements of pre- and post-cycled pow-
(NO3)3⋅9H2O were prepared with appropriate molar ratios and pumped der-type pellet cells were acquired to probe changes in the crystal
into a 10 L continuously stirred tank reactor under a nitrogen atmo- structure of the active material. Data was acquired using a Rigaku Smart
sphere. Aqueous solutions of KOH and NH4OH were simultaneously fed Lab diffractometer with a D/teX Ultra 250 1D detector and Cu Kα X-ray
into the reactor to control the pH and precipitation rate. The reactor source. All samples were prepared inside an argon glovebox and placed
temperature, pH, and stir rate were carefully controlled throughout the in an air-free holder for XRD analysis. 2-theta scans were taken using a
reaction. After the reaction, the resultant Ni0.9Mn0.05Al0.05(OH)2 pow- divergence slit of one-fourth, an anti-scatter slit of 1, and a 10 mm mask.
der was washed thoroughly, vacuum-filtered, and dry overnight at
100 ◦ C. Finally, LiNi0.9Mn0.05Al0.05O2 (NMA) was synthesized by mixing 2.4. X-ray photoelectron spectroscopy
the mixed-metal hydroxide precursor with LiOH⋅H2O in a molar ratio of
1:1.01 and subsequently calcining at 760 ◦ C for 12 h under O2 flow. X-ray photoelectron spectroscopy (XPS) measurements were per-
formed using a Physical Electronics Phi VersaProbe III with mono-
2.2. Cell fabrication and electrochemical testing chromatic Al Kα X-ray excitation (hν = 1.487 keV). The instrument was
calibrated to Cu 2p3/2 at 932.62 eV and Au 4f7/2 at 83.96 eV. XPS data
Two types of cells were constructed for the work described in this processing and curve fitting were carried out using a custom program
manuscript: 1) “powder-type” or pellet-cell cells which were cycled in- based on Igor Pro Software previously described [44]. The net positive
side a pellet-press setup, and 2) coin cells which were used for electro- charge applied to delithiate the NMA cathode during the virtual elec-
chemical impedance spectroscopy (EIS) characterization. All cell trode X-ray photoelectron spectroscopy (VE-XPS) experiment was
fabrication was conducted in an argon filled glovebox with <0.1 ppm accomplished using UV photons (He–I, hv = 21.22 eV) supplied by a
H2O. helium lamp (Physical Electronics Model 04–900). The VE-XPS method
For powder-type cells, the catholyte consisted of 55 wt% NMA, 44 wt used here was described in detail by Wood et al. previously [45]. The
% chlorinated argyrodite (Ampcera Argyrodite Li6PS5Cl Sulfide Solid NMA||LPSC||silicon cells were fabricated using the same method as the
Electrolyte, Pass 325 mesh D50 < 10 um), and 1 wt% vapor grown powder-type cells outlined above. The cells were disassembled from the
carbon fiber (VGCF, Sigma-Aldrich DxL 100 nm × 20–200 nm). Com- custom pellet-press after was 350 MPa applied and removed for VE-XPS.
ponents (~2 g) were ground in a mortar and pestle for 45 min to achieve Ball milling of the NMA cathodes to increase their surface area was
3
accomplished in a zirconia vessel with 3 mm diameter zirconia milling 2.7. Nanocomputed tomography
media in a Retsch PM 200 planetary mill at 450 rpm for 75 min as
described previously [46]. Nano X-ray computed tomography (nano CT) was used to image the
catholyte both before and after being pressed to 350 MPa. The catholyte
was prepared by placing the material into 100 μm outer diameter cap-
2.5. Attenuated total-reflectance fourier transform infrared spectroscopy illaries inside a glovebox. The capillaries loaded with pristine and
(ATR-FTIR) pressed catholyte powder were imaged using a lab-based nano-CT in-
strument (Zeiss Xradia 810 Ultra, Carl Zeiss) with a quasi-
A Bruker Invenio FTIR spectrometer equipped with a monolithic monochromatic X-ray energy of 5.4 keV. The images were taken with
diamond ATR crystal and room-temperature DTGS detector was used to a pixel binning of 2 and a pixel size of 128 nm to obtain a field of view of
collect vibrational absorption spectra of dry powder cathode materials 64 μm × 64 μm. The catholyte samples were rotated through 180o and
(55 wt% pristine NMA, 44 wt% LPSC, 1 wt% VGCF), uncycled NMA radiographs were collected at 0.163o intervals, resulting in a total of
cathode, and cycled NMA cathode. The cycled cell was a powder-type 1101 projections. Absorption contrast was used to image the catholyte
cell described above which had undergone 25 cycles at either C/20 or samples. The raw radiograph images were reconstructed using a com-
C/4. To avoid exposure to air, the samples were prepared in an argon- mercial software package (Reconstructor Scout-and-Scan, Carl Zeiss).
filled glovebox (<0.1 ppm H2O). The samples were sealed inside a The visualization of the images was carried out using Dragonfly
coin cell cap atop the monolithic diamond ATR crystal as previously (2022.2.0.1409, Object Research System).
described [47]. The samples were then removed from the glovebox for
FTIR measurements. IR spectra were collected with a resolution of 4 3. Results and discussion
cm− 1 and a 32-scan average.
3.1. Electrochemical
2.6. Confocal Raman microscopy
The electrochemical results of a high-loading (4.9 mAh/cm2), all-
solid-state, NMA||LPSC||Si thin-film hybrid cell are shown in
Raman scattering spectra of the NMA and silicon interfaces with
Fig. 1a–d. The initial discharge capacity indicates 92 % NMA utilization
LPSC electrolyte from NMA||LPSC||silicon cells, cycled and uncycled,
at C/20 discharge (1C = 180mAh/g). The differential capacity plots
were acquired using a Renishaw inVia confocal Raman microscope with
reveal the anticipated NMA H3 to H2 phase transition, followed by the
a 532 nm, 100 mW (RL532C100) laser source and a Leica N Plan EPI
H2 to monoclinic phase (more below). Furthermore, the CC discharge
20×/0.4NA objective. Spectra were collected in the range of 50–1835
capacity of the faster C/4 rate is only 10 % less than the C/20 rate,
cm− 1 using an 1800 g/mm diffraction grating, a 532 nm notch filter, 1 %
suggesting that the cell has low overall impedance. This was confirmed
laser power, 5 s exposure time, and 12 accumulations (60 s total
with the electrochemical impedance spectroscopy (EIS) spectra seen in
acquisition time).
Fig. 1. a) The specific discharge capacity in mAh/g and columbic efficiency by cycle number for a 4.9 mAh/cm2 NMA–Si cell cycled at room temperature and 180
MPa stack pressure. b) Voltage profiles and Electrochemical impedance spectroscopy (c) of the NMA–Si cell after 25 cycles showing low overall cell resistance. Inset
shows high frequency region. d) Differential capacity plot for the first two cycles for the same NMA-Si cell shown in (a).
4
Fig. 1c taken after 10 cycles at approximately 50 % state-of-charge. An then shifts from the M phase to H2 near 3.75 V and starts the H2 to H3
80 % state-of-health was reached after 25 cycles. This rapid capacity phase transition above 4.1 V. The lack of oxidation below 3.5 V on the
fade represents a tradeoff between high initial capacity and overall ca- first charge suggests that electrolyte degradation caused by high surface
pacity retention which is discussed in more detail in the characterization area carbon contact has largely been avoided [16]. The H1 to M phase
section to follow. This all solid-state, Ni-rich cell performs well when transition can often present as two separate peaks, it is believed that they
compared to the large range of specific discharge capacities reported in present as a single peak here because they are obscured by the likely
the literature (from 90 to 190 mAh/g) for similar cell chemistries, spe- significant LPSC decomposition that occurs above 2.9 V. While the H1 to
cifically, its high initial discharge of 213 mAh/g and 750 Wh/kg at room M and M to H2 oxidation peaks can clearly be seen in Fig. 1d, only the
temperature [7–9]. start of the H2 to H3 phase transition can be seen in this plot because the
Notably, the NMC‑silicon cell exhibited a poor coulombic efficiency cell underwent a voltage hold at 4.2 V (DV ~0) so it was removed for
(CE) as shown in (Fig. 1a) despite a high first-cycle discharge capacity easier viewing. On reduction, the phases reverse in order and present as
(213 mAh/g). The coulombic efficiency (CE) is near 100 % at C/20 but three peaks at 3.9, 3.7, and 3.25 V. Surprisingly, the H3 to H2 reduction
remains low (approximately 80 %) for the C/4 cycling rates without the peak (3.9 V) has decreased significantly from the 1st to the 2nd cycle.
expected decrease in the overall charge/discharge capacity (if all the CE This may be because the voltage cutoff for the cell at this stage was 4.2 V
could be attributed to active material loss or irreversible lithium in- and overpotential caused by LPSC degradation during the 1st cycle kept
ventory consumption, there would be a C/20 discharge capacity of <25 the cathode from fully reaching the H2 to H3 oxidation potential, evi-
mAh/g after ten cycles.). This discrepancy – while concerning – does not denced by the early onset and diminished area under the H2 to H3
prevent the cell from reaching top-of-charge voltage, having reasonable oxidation peak for the 2nd cycle. This, coupled with the specific
discharge capacities, and having “noisy” voltage profiles [48,49]. It can discharge capacity, suggests that NMA
likely be attributed to soft shorting, or more specifically, transient cathodes do not display obvious differences in electrochemical
lithium dendrites that form and degrade as the cell is cycled [31]. Three- behavior compared to typical nickel-rich NMC cathodes in all solid-state
electrode measurements for similar cell chemistries show low potentials cells using argyrodite electrolytes [53].
at the silicon anode on charging—near lithium’s plating potential [50] Full NMA||LPSC||Si coin cells were fabricated, and electrochemical
— subjecting the cell to soft short conditions. It’s possible that the cell impedance spectroscopy (EIS) was conducted as a function of state-of-
also suffers from partially reversible LPSC redox activity when in contact charge (SoC) to gain additional information into the behavior of this
with electrically conductive carbon reducing its CE, reported previously system. The 1st formation cycle was performed at a C/20 rate with
[23]. A cell capable of operating at such low CEs and reasonably high potentiostatic EIS interruptions every 30 min and 10-min rests. Fre-
capacities warrants further study outside the scope of this text. quencies were swept from 1 MHz to 10 mHz with an AC amplitude to of
To gain insight into the electrochemical behavior of the NMA|| +/− 10 mV. Insets on each figure contain the high-frequency portions of
LPSC||Si cells, differential capacity data are analyzed (Fig. 1d) for the the spectra. The EIS spectra for the 1st charge cycle have been broken
1st and 2nd cycle for the cell. Typically, NMA cathodes display similar down into 3 sections for ease of viewing. The 1st section corresponds to
redox activity in differential capacity plots when compared to other the low-voltage region (<3.5 V), and the 1st spectra in this panel
nickel-rich NMC-type cathodes and the features of NMC-type cells con- occurred at 0.7 V (a table of voltages and SoC vs time can be seen in
taining silicon anodes are often dominated by the cathode’s redox peaks Fig. S1). In general, full cell solid-state batteries can be qualitatively
[11,51,52] Oxidation peaks begin above 3.5 V with lithiation of silicon assessed assuming processes are presented from high to low frequency
and NMA H1 to M phase transition (hexagonal to monoclinic phase) and as: RSSEb and RSSEgrain which are the resistance of the bulk and grain
Fig. 2. Electrochemical impedance spectroscopy (EIS) plots taken during the 1st charge (c–d) and 1st discharge (e,f). Cell potential vs time plots for the 1charge and
discharge (a) detail where in the charge/discharge profile the EIS plots were taken. More detailed EIS graphs can be seen in fig. S2 and S3. Additional electrochemical
cycling data can be seen in Fig. S4.
5
boundaries of the solid-state electrolyte, Ranode and Rcathode which are frequency peak expands and evolves into multiple features (Fig. 2d).
the resistances of the anode and cathode electrode composites, and While NMC-type cathodes have small changes (<30 Ohm/cm2) in their
constant phase element or Warburg element to capture diffusion into the resistance measured by EIS above 80 % SoC, silicon anodes do have large
electrodes [54]. changes (>300 Ohm/cm2) [58,59]. This observation suggests that the
Starting with the first charge, a large resistance of 90 kΩ is present at silicon anode approaches full lithiation above 4.12 V. This would be
low cell potential (<0.75 V) that corresponds to pristine silicon and a remarkable because the N:P ratio (ratio of the negative electrode to that
fully lithiated cathode [55]. A rapid decrease in the overall cell resis- of the positive) of 1.13 would make it impossible for the cathode to fully
tance occurs quickly upon initial charging as the silicon begins to lith- lithiate the anode alone, suggesting additional lithium was made
iate. The next EIS spectrum occurs at a cell potential of 3.40 V and shows available from LPSC degradation at the cathode [60].
a collapse of the overall cell potential to 4 kΩ. Two semicircles are The 1st discharge EIS can be seen in Fig. 2e–f. Here, the high-
present at voltages below 4.05 V. A large portion of the second semi- frequency semicircle expands slightly while the low-frequency semi-
circle (in the low frequency range) can be attributed to the pristine sil- circle increases to a greater extent. This remains the case until ~3.5 V is
icon electrode which begins to lithiate at 0.2 V vs Li which corresponds reached (54 % SoC). Below 3.5 V, both the low and the high-frequency
to an overall cell potential >3.4 V [56]. Both semicircles decrease as the semicircles increase in size. As the voltage decreases, the low-frequency
SoC increases beyond 10 % from 3.55 to 4.05 V, which is common for semicircle disappears, the Warburg tail vanishes and a large semicircle
both NMC-type cathodes and silicon anodes [57,58]. The low-frequency with a resistance of ~2 kΩ appears. This appears similar to Fig. 2b when
semicircle diminishes to reveal the Warburg tail and the high-frequency the voltage was 3.40 V. Much speculation exists about the physical
semicircle decreases from ~300 Ohm to ~150 Ohm. Above 4.05 V (70 % processes at play during the 1st cycle of this NMA||LPCS||Si cell. There
SoC), the high-frequency semicircle remains static, and the low- are aspects of the spectra that are strikingly similar to cells reported in
Fig. 3. Fourier Transform Infrared Spectroscopy data (a–d) showing select wavenumber ranges corresponding to the major electrolyte degradation peaks for both
uncycled and cycled catholyte material containing NMA cathode and LPSC electrolyte. Raman spectra comparing pristine and cycled (e) NMA-LPSC interface and (f)
Silicon-LPSC interface. Intensity has been normalized to the PS3− − 1
4 stretching mode intensity at around 425 cm . The full FTIR and Raman spectra can be seen
in Fig. S5.
6
the literature. Ke Pan et al. performed Distribution of Relaxation Times the cycled spectrum is evidence of LPSC degradation into P2S2−
x with a
(DRT) for several Si–Si, Li–Si and Li–Li cells in order to deconvolute peak at 386 cm− 1, like what was found at the catholyte.
different processes from the EIS data. The authors assigned DRT peaks
P1, P2, and P3 to the high-frequency contact loss process, SEI diffusion
process, and charge transfer kinetics, respectively. They demonstrated 3.3. X-ray diffraction
that the charge transfer kinetics shows the largest variation with SoC,
because the charge transfer kinetics follows the Butler-Volmer equation To probe the crystal structure of the cathode material after cycling,
which is strongly dependent on the lithium concentration at the Si- X-ray diffraction data was collected for both uncycled catholyte and
electrolyte interface [58]. These trends follow closely to what is re- catholyte that had seen 25 cycles of 2.8–4.3 V. The sample that had seen
ported here, and strongly suggests that the change in the low-frequency electrochemical cycling was fully discharged (NMA fully lithiated)
semicircle can be attributed to the change in charge transfer kinetics at before being disassembled in an argon filled glovebox and placed into an
the silicon anode with SoC or interfacial decomposition of the LPSC, air-free holder. The Rigaku SmartLab system contained a Cu Kα X-ray
which would introduce new charge transfer interfaces in the impedance source.
spectra. The results are plotted in Fig. 4. The diffractogram of the silicon
anode can be seen in Fig. 4a. The 111, 220, and 311 peaks of crystalline
3.2. Fourier transform infrared spectroscopy silicon can be seen for the uncycled material. Upon cycling, the silicon
amorphized and its XRD peaks disappear with only the peaks of the Cu
The FTIR spectra of cycled and uncycled NMA-LPSC catholytes substrate visible. This suggests that although the N:P ratio for the cell
(Fig. 3) show profound degradation of the LPSC electrolyte in the cycled was 1.13, much of the silicon was lithiated in the course of 25 cycles.
cell. Two main degradation pathways have been identified for the LPSC The diffractogram of the catholyte demonstrates a phase pure NMA
SSEs, electrochemical and oxygen-involving [40]. Electrochemical cathode consistent with that found in the literature [11] and appears to
degradation of the LPSC readily occurs with the most common cathode remain highly crystalline after cycling as evidenced by the splitting of
and anode pairings due to its limited electrochemical stability window the 018/110 peaks [65]. Although the NMA in both samples is fully
(~1.07–2.01 V) [21]. This pathway yields degradation products such as lithiated, peak shifts in the 003, 101, 104, and 018/110 peaks suggest
LiCl, P2S5, P, and sulfur. Oxygen-involving decomposition can occur that lithium has been consumed in the cell. The peak shifts expected of a
whenever there is an oxygen source available and yields degradation
products like LiCl, phosphates, sulfites, and sulfates. There are several
sources of oxygen available for oxidative decomposition: oxygen
released from the cathode active material, organic species on the SSE
material, or water absorbed to any of the cell components [40].
The absence of a broad peak near 3000 cm− 1 (Fig. 3a) suggests that
there is no water absorbed to the material. While there is no evidence of
water in the material, XPS data (Fig. 5c) shows that there is indeed
oxygen present in the catholyte (discussed below). The presence of
sulfur oxides can be seen at 975 and 1300 cm− 1 (Fig. 3c, b) in the cycled
material. It is unclear if oxygen evolving from the NMA cathode caused
the sulfate formation but there is no indication of structural reformation
associated with oxygen release from NMA (discussed below). Carbonate
anion asymmetric stretching (1425 cm− 1) and out-of-plane bending
(865 cm− 1) can be seen in both samples, suggesting the formation
Li2CO3 [61] or from carbonate moieties within the VGCF additive. The
peak at 1030 cm− 1 and 567 cm− 1 represents vibration of PO4 group that
is present in the pristine material [42,62]. It is likely that the broad peak
shown in the Fig. 3d uncycled spectra represents a convolution of PO4
and PS4 signals or some mixture of partially hydroxylated thio-
phosphates. This suggests that some Li3PO4 and Li2CO3, contamination
may be present in the pristine material as potential the oxygen sources.
The absence of the PO4 group vibrational modes post-cycling can be
attributed to different stoichiometric ratios of other LPSC decomposition
products such as SxO, P2S5 and LiCl-related species which can reduce the
number of phosphates present [40].
Although FTIR measurements show a disappearance of the PS3− 4
argyrodite moiety upon cycling, more-sensitive Raman scattering
spectra of the catholyte (Fig. 3e) shows persistence of the this chemical
group symmetric vibration but with a shift to lower energies from 427 to
424 cm− 1 and 580 to 550 cm− 1 upon cycling [63]. Also evident in the
cycled sample spectrum are Li2Sx>2 LPSC decomposition products at
460 cm− 1. A small peak ~475 cm− 1 can be attributed to S–S dimers can
be seen in the cycled catholyte but not at the anode [64].
The silicon anode interface with the LPSC was also characterized by
Raman (Fig. 3f). The pristine sample shows a clear peak of crystalline
silicon at 521 cm− 1 that is not existent after cycling. This indicates Fig. 4. X-ray diffraction data showing the diffractogram for both the silicon (a)
lithiation of the silicon occurred during charging and amorphous silicon and catholyte (b-e) sides of a NMA–silicon solid-state pellet before cycling
was formed after discharging. The broad amorphous silicon peak ex- (uncycled) and post-cycling (cycled). Panels b-e show the prominent peaks of
pected around 470 cm-1 in the cycled sample is likely obscured by the the NMA active material and suggest that lithium loss has occurred after
strong PS3− − 1
4 stretching mode absorption at 427 cm . Also noticeable in cycling. The full 2 theta range for the catholyte can be seen in Fig. S6.
7
partially delithiated NMA-type cathode material are denoted in the spectroscopy (XPS) spectra were taken of 5 samples (Fig. 5). XPS studies
figure with red arrows. This suggests that a non-trivial amount of lithium were either conducted ex-situ (Fig. 5e–h) or via virtual electrode X-ray
loss occurred after 25 cycles which, as discussed above, could be the photoelectron spectroscopy (VE-XPS in Fig. 5a–d) which has been used
formation of dead lithium (from hard or soft shorts) that is encouraged to study other solid-state systems and described previously [42,45].
to form at the high cycling pressures used in this study [30], lithium The samples for the VE-XPS (Fig. 5a–d) were prepared identically to
irreversibly bound in the silicon anode as trapped lithium which can the powder-type hybrid cells in Fig. 1. The catholyte of the powder-type
account for ~40 % of the lithium loss in Li–Si cells, or the conversion of cells was illuminated with a UV light source to liberate electrons, thus
LPSC into higher lithium content stoichiometries such as, Li2S, Li3P, or creating a positive charge, which delithiates the NMA particles. The
LiCl as we have reported previously [66]. spectral series is taken as the charge in the cathode increases, with the
pristine spectra at the bottom. The ex-situ samples (Fig. 5e–h) contain
3.4. X-ray photoelectron spectroscopy (XPS) uncycled and cycled catholyte mixtures that have NMA in one of two
morphologies, pristine and ball-milled. The purpose of the ball milling is
To further probe the NMA-argyrodite interface, X-ray photoelectron to maintain the chemistry of the NMA while increasing its surface area
Fig. 5. A VE-XPS experiment on the NMA portion of a NMA vs Si ASSB (a–d). The series shows increasing charge with the pristine catholyte at the bottom. Ex-situ X-
ray photoelectron spectroscopy data showing spectra from both cycled (C-NMA) and uncycled (U-NMA) catholyte for the P2p, S2p, O1s, and C1s (e–h) binding
energies. Samples names with “BM” signify catholyte materials that contain NMA particles that were ball milled to increase their surface area-to-volume ratio before
being mixed with LPSC and carbon. XPS data of pristine NMA powder can be seen in Fig. S7.
8
and thus the NMA-argyrodite interface. The NMA was milled according from this data, but additional experiments may reveal both the exact
to the method described previously [46]. The uncycled material is mechanism of their disappearance and the connection between car-
denoted as U-NMA. NMA that had been ball-milled before it was formed bonate anions and phosphate and/or sulfate formation. If the formation
into a catholyte is denoted U-BM-NMA. Catholyte material that had been of phosphate is indeed caused by the decomposition of lithium car-
cycled for one cycle at a rate of C/20 between 2.9 and 4.3 V is denoted C- bonate, it should be accompanied by the release of carbon monoxide or
NMA and C-BM-NMA. dioxide species. There is some evidence in the literature as to the origin
The XPS spectra show that the argyrodite SSE is nearly pristine of uncharged (–S0– groups) sulfur species. Anion polysulfide forma-
before cycling. The binding energies for the P2p, S2p, O1s, and C1s tion (P–[S]n–P-type) with increasing values of n, or the number of
(Fig. 5) spectra are consistent with Li6PS5Cl and there was no discern- bridging sulfur atoms, will have increasing number of uncharged sulfur
able change in the Cl 2p signal [67]. This includes oxygen contamination species that will result in the doublet at higher binding energies that
present in the pristine argyrodite [68]. The pristine material seems to depend on the polysulfide chain length [28]. Almost all of the degra-
contain at least some phosphate before cycling in agreement with the dation species discussed here contribute to overall cell resistance, except
FTIR data shown above. The pristine sample also shows evidence of for possibly the phosphate species. Several approaches may be consid-
residual Li2S precursor which recedes on cycling (Fig. 5b, f). After ered to limit cathode–SSE degradation, including mixed SEE species to
cycling, the cathode–SSE interface decomposes into expected phases: make stable interfaces with lithium metal, LiF-Li3N protective layers,
P2Sx, uncharged sulfur species, and phosphates [67]. Ball-milling results and AgI alloy inducing films [71–73].
in more phosphates at the cathode–SSE interface than the untreated
sample, which is likely due to the higher surface area. The areas of the
3.5. Nanocomputed tomography
phosphate peaks in the P2p (135.7 eV) and O1s (535.0 eV) core levels
are >3× larger than the untreated sample, suggesting that this process
Cross-sections of pre- and post-consolidated catholyte powders are
indeed occurs at the cathode–SSE interface and that oxygen from the
shown in Fig. 6. In these images, lighter colors represent higher X-ray
NMA surface may play a role as in other nickel-rich NMC-type cathodes
attenuation coefficients. Hence, NMA particles appear white due to their
[69,70].
higher effective atomic number (and therefor higher attenuation coef-
One phenomenon to highlight is the disappearance of the carbonate
ficient) in comparison to LPSC particles or pores which are dark grey and
anion from Li2CO3 (Fig. 5c, g). Specifically, the carbonate anion di-
not sufficiently resolved by this diagnostic. The pre-consolidation NMA
minishes on cycling while the other oxygen containing species remain
particles seen in Fig. 6a–d are generally round with the expected size
unaffected. Interestingly, this corresponds to the increasing signal
distribution (approximately 10 μm.). In contrast, severe cracking or
strength of the phosphate species (Fig. 5a, e). This suggests that the
fracturing is observed (yellow dashed circles) in the NMA particles of the
oxygen source for phosphate formation on cycling may be carbonates
post-consolidation catholyte (Fig. 6e–i) [46]. The fracture of the sec-
from either the argyrodite or the NMA surfaces (Fig. S7). There is a slight
ondary structure of the NMA particles is similar to the fracturing that
discrepancy between the FTIR and XPS data on this matter that may be
occurs when calendering electrodes to low-porosity (<30 %) which can
attributed to the difference in penetration depth between the methods.
cause decrease capacity retention [74]. While calandering can exert
Interestingly, there appears to be some phase segregation of the degra-
pressures >50 MPa, much higher pressures are routinely used to
dation products when examining cross-sectional images of cycled pellet
consolidate ASSBs [75]. Hence, it is reasonable to assume that me-
cells with energy-dispersive X-ray spectroscopy (Fig. S8). These images
chanical damage to active material particles is prevalent across various
suggest that there may be some migration of degradation species which
catholyte compositions when high consolidation-pressures are used.
could lead to differences in spectroscopic data when comparing results
Fabrication pressures typically used for pellet-type cells in the literature
from methods with different penetration depths. The contaminant Li2O
exceed 300 MPa and are most likely inflicting significant damage the
peak disappears after cycling in the ball-milled sample. As the cath-
secondary structure of the nickel-rich cathodes. The results from the
ode–SSE interface degrades during cycling, these phases either decom-
nano CT indicate that fabrication pressures must be limited to prevent
pose or are covered up by the new phases that form. It is difficult to tell
cathode fracturing. New methods for catholyte consolidation may be
Fig. 6. Nanocomputed tomography images showing cross-sections of catholyte materials (a–d) and catholyte materials that had been pressed to the fabrication
pressure of 350 MPa (e–i). The NMA particles are shown in white and appear spherical in the unpressed sample (a–d) and fractured (yellow dashed circle) in the
pressed sample (e–i). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
9
necessary to produce films that limit cathode cracking while achieving Conceptualization. Ryan Tancin: Writing – review & editing, Writing –
ionic conductivities that mostly require high fabrication pressures at this original draft, Formal analysis. Glenn Teeter: Visualization, Method-
moment. ology, Formal analysis, Data curation. Gabriel Veith: Writing – review
& editing, Formal analysis, Data curation. Bertrand J. Tremolet de
4. Conclusion Villers: Writing – review & editing, Writing – original draft, Visualiza-
tion, Formal analysis, Data curation. Andrew Colclasure: Writing –
A high-loading (~5 mAh/cm2) all-solid-state pellet cell containing a review & editing, Project administration, Methodology, Funding
no-cobalt NMA cathode and 99 wt% silicon anode has been reported for acquisition, Formal analysis, Conceptualization. Arumugam Man-
the first time. This cell had an impressive initial discharge capacity at thiram: Supervision, Project administration, Investigation, Data
room temperature >210 mAh/gNMA at C/20 charge/discharge rate and curation.
178 mAh/gNMA when cycled at a rate of C/4. Electrolyte degradation
closely resembled that of other nickel-rich transition metal oxide cath- Declaration of competing interest
ode materials, suggesting the NMA does not cause superfluous electro-
lyte degradation. The argyrodite solid electrolyte degrades via The authors declare the following financial interests/personal re-
electrochemical and oxygen-involving pathways in our experiments. lationships which may be considered as potential competing interests:
Specifically, it is shown the carbonate anion from Li2CO3 on the NMA or Ryan Brow reports financial support was provided by National Renew-
argyrodite surface may be the oxygen source for phosphate formation able Energy Laboratory. Ryan Brow reports financial support was pro-
for the first time. The NMA cathode shows extensive fracturing after the vided by Vehicle Technologies Office. Arumugam Manthiram reports a
application of the 350 MPa fabrication pressure. Future studies should relationship with TexPower Inc. that includes: board membership and
limit oxygen contamination on the surface of cathodes or in the solid equity or stocks. If there are other authors, they declare that they have
electrolyte that may promote electrolyte degradation and decrease ca- no known competing financial interests or personal relationships that
pacity retention. Careful consideration should be applied when choosing could have appeared to influence the work reported in this paper.
fabrication pressures for pellet-type cells. The high fabrication pressures
commonly used for bench-scale experiments can lead to extensive Data availability
cathode active material particle fracture which can lead to dramatic
capacity fade. It’s critical for studies to more thoroughly explore the Data will be made available on request.
balance between achieving intimate contact between the cathode active
material and the electrolyte, and the risk of damaging the active mate-
Acknowledgments
rial through excessive pressure.
This work was authored in part by the National Renewable Energy
Funding
Laboratory (NREL), operated by Alliance for Sustainable Energy, LLC,
for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-
This work was authored in part by the National Renewable Energy
08GO28308. This work was supported by the U.S. Department of En-
Laboratory (NREL), operated by Alliance for Sustainable Energy, LLC,
ergy. This research was supported by the U.S. Department of Energy’s
for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-
Vehicle Technologies Office under the Advanced Battery Materials
08GO28308. Funding provided by the U.S. Department of Energy’s
Research (BMR) Program, directed by Simon Thompson and Tien
Vehicle Technologies Office (VTO) under the Low-Pressure All-Solid-
Duong. The views expressed in the article do not necessarily represent
State Cells project directed by Simon Thompson and Tien Duong and
the views of the DOE or the U.S. Government. The U.S. Government
managed by Anthony Burrell. The views expressed in the article do not
retains and the publisher, by accepting the article for publication, ac-
necessarily represent the views of the DOE or the U.S. Government. The
knowledges that the U.S. Government retains a nonexclusive, paid-up,
U.S. Government retains and the publisher, by accepting the article for
irrevocable, worldwide license to publish or reproduce the published
publication, acknowledges that the U.S. Government retains a nonex-
form of this work, or allow others to do so, for U.S. Government
clusive, paid-up, irrevocable, worldwide license to publish or reproduce
purposes.
the published form of this work, or allow others to do so, for U.S. Gov-
ernment purposes.
Appendix A. Supplementary data
Notes
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.est.2024.113329.
The authors declare the following competing financial interest(s):
One of the authors (A. M.) is a co-founder of TexPower, Inc., a start-up
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Journal of Energy Storage 99 (2024) 113329

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Journal of Energy Storage

Cobalt-free cathodes and silicon thin-film anodes towards high-capacity

1. Introduction and a less-reactive silicon anode.

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