TBM-129 LNMO cathode and XNOTM anode

White paper

DEVELOPING A
HIGH-PERFORMANCE,
COBALT-FREE,
3V BATTERY CELL
BASED ON HIGH-VOLTAGE SPINEL (LNMO)
CATHODE AND MIXED NIOBIUM OXIDE
(XNO) ANODE

Prepared by:
Harry Geary2, Christian Fink Elkjær1, Loubna El Ouatani2, Joris Pezin2, Benjamin Ting2,
Frederik Flemming1, Jeppe Winther Hedegaard1 and Jonathan Højberg1
1
Haldor Topsoe A/S, Denmark, 2 Echion Technologies, United Kingdom
CONTENTS

1. INTRODUCTION 3

2. LNMO AND XNO ELECTROCHEMICAL PROPERTIES 4

3. LNMO–XNO FULL CELL 5

4. COMMERCIAL-FORMAT CELL MODELLING 7

5. APPLICATION OUTLOOK 8

6. FINAL MESSAGE 8

7. METHODS 9

TBM-129 LNMO cathode and XNOTM anode TO CONTENTS 2

1.
INTRODUCTION
The use of the higher-voltage anode material, XNO,
Lithium-ion batteries are widely accepted as the allows for faster charging compared to graphite
energy-storage norm, and are expected to become anodes, and higher-capacity retention at fast charging
the primary energy source for a more diverse range rates compared to LTO. The high-voltage LNMO spinel
of mobile and stationary applications over the next material increases the average cell voltage of systems
decade. However, current Li-ion technology cannot using XNO anodes from 2.2 V to 3 V, compared to
satisfy the charge-speed and cycle-life requirements NMC-type materials. The system does not allow lithium
needed to achieve widespread acceptance in markets plating or overcharging, making it inherently safer than
like rail, micro-transport, and e-ferries. cells whose chemistries include graphite or NMC-type
materials.
A Li-ion cell’s performance is the result of careful
interplay between its various components, guided by The LNMO-XNO cell’s 3 V nominal voltage unlocks a
active materials, cell design, and voltage limits. With range of use cases, and allows for easy integration
these factors in mind, Topsoe and Echion Technologies without requiring an expensive redesign of existing
have developed a cobalt-free 3 V system designed for power electronics. Topsoe’s collaboration with Echion
fast charging, optimal safety, and maximum cycle life by focuses on applying new innovations that enable
combining a LiNi0.5Mn1.5O4 (LNMO) spinel cathode and an high-powered, long cycle-life cell systems to push
Nb-based XNO anode. boundaries in terms of applicationspecific requirements
for safety, power, energy density, and temperature-
based performance.

TBM-129 LNMO cathode and XNOTM anode TO CONTENTS 3

2.
LNMO AND XNO ELECTROCHEMICAL PROPERTIES
When designing the LNMO-XNO system, it was delithiation.
important to consider the electrochemical behaviour of
the two individual materials compared to that of Li/Li+ in Figure 1(C) shows a first-formation cycle for the LNMO
half-cells with lithium-negative electrodes. This allowed cathode, with initial delithiation to 5 V vs. Li/Li+, followed
for an investigation of material properties like voltage by lithiation to 3.5 V vs. Li/Li+. Delithiation of LNMO
profiles, first-cycle efficiencies, specific capacity values, comprises three electrochemical reactions:
and charge/discharge rates. Mn3+ oxidizing to Mn4+ at around 4 V; Ni2+ oxidizing
to Ni3+ at 4.7 V; and Ni3+ oxidizing to Ni4+ at 4.75 V.
Figure 1(A) shows the first-formation cycle for the XNO The exact shape of the voltage profile depends on
anode, with initial lithiation to 1.1 V vs. Li/Li+, followed the composition and crystal structure of the LNMO,
by delithiation to 3.0 V vs. Li/Li+. The material exhibits a explained in greater detail in previous work from
high first-cycle efficiency of 98.5%, due to a very low Topsoe1.
degree of Li-ion trapping within the crystal structure
upon delithiation. This is due to the open nature Figure 1(D) shows a lithiation-rate test of LNMO at room
of Nb-containing, Wadsley-Roth block structures, which temperature, corresponding to discharge of a full cell
facilitates extremely fast Li-ion diffusion. The Nb5+/3+ containing LNMO cathode material. The delithiation rate
redox couple also enables a high voltage capacity above is low at 0.5 C, and LNMO retains capacity of around
1 V, thereby preventing SEI formation. 80% at 10 C lithiation.

Figure 1(B) shows an XNO delithiation-rate test at room

temperature, corresponding to discharge of a full cell
containing XNO anode material. The lithiation rate is
low at 0.1 C, and XNO retains almost full capacity at 10 C

FIGURE 1:

A B

C D

(A) First-formation cycle of XNO-anode material in a half-cell, demonstrating reversible capacity of 215 mAhg-1 and 98.5% first-cycle efficiency.
(B) Delithiation-rate test of XNO-anode material in a half-cell, demonstrating 95% capacity retention (vs 0.5 C) at 10 C and 70% at 20 C. Tests were conducted
in coin cells, with an electrode composite loading of 1.4 mAhcm-2.
(C) First-formation cycle of LNMO-cathode material in a half-cell, demonstrating reversible capacity of 137 mAhg-1 and 95% first-cycle efficiency.
(D) Lithiation-rate test of LNMO-cathode material in a half-cell, demonstrating 80% capacity retention (vs 0.5C) at 10 C. Tests were conducted in coin cells at 25°C,
with electrode composite loadings of 1.1 mAhcm-2.
1
.[Characterization of high-voltage Li1.0Ni0.5Mn1.5O4 and correspondence between Ni content in spinel, lattice size, and 4 V capacity.
https://www.topsoe.com/industries/batteries].

TBM-129 LNMO cathode and XNOTM anode TO CONTENTS 4

3.
LNMO–XNO FULL CELL

Figure 2(A) shows the first-formation cycle of an Figure 2(B) shows the charge- and discharge-rate
LNMO-XNO battery recorded in a 3-electrode cell, with performance of the LNMO-XNO coin cell. As expected
an Li reference used to follow the individual potentials from the half-cell results, discharge performance was
of the cathode and anode during charge and discharge. excellent: when discharging at 10 C, 86% of capacity
An extended voltage interval of 1.5–3.8 V was used to was retained. Chargerate performance is lower than
explore the full voltage window. To optimize cycle life, the discharge rate, but the LNMO/XNO system still
however, cathode voltage should not exceed 5 V while demonstrates up to 80% retention at 5 C, and 68%
maintaining a high usable capacity; an upper cut-off of retention at 10 C.
around 3.5 V is optimal for this specific N/P ratio.

FIGURE 2:

(A) First-formation charge-discharge

voltage curve of LNMO-XNO full cell
and the individual cathode and anode
voltages, displaying a full cell nominal
voltage of 3 V.

(B) Charge and discharge rate

performance of LNMO-XNO full
coin cell. All tests conducted at 25°C.

TBM-129 LNMO cathode and XNOTM anode TO CONTENTS 5

In addition to excellent rate performance, the
LNMO-XNO system exhibits very good cycling stability.

Figure 3 shows the development in 0.1 C-discharge

capacity (measured every 50 cycles), over 1000 cycles,
when cycling between 2.5 V and 3.5 V at 1 C. Under
these conditions, the system retains 93% of its initial
capacity after 1000 cycles. This result was achieved
through use of a standard electrolyte without any
additives, and further improvement to overall cycle life
can be expected with additional optimization of the
electrolyte formula.

FIGURE 3:

Figure 3. Cycle life of LNMO-XNO full coin cell

at 25°C. The plot shows reference capacity
checks at 0.1 C measured every 50 cycles.

TBM-129 LNMO cathode and XNOTM anode TO CONTENTS 6

4.
COMMERCIAL-FORMAT CELL MODELLING

Echion used a model wherein LNMO/ XNO performance When comparing these new systems to graphite-based,
was compared to three other systems: NMC/LTO, NMC/ high-power Liion cells, it is important to note that
XNO, and LNMO/LTO. while the latter are certainly capable of high-discharge
power, they are severely limited in lifetime and charge
Figure 4 shows various cell designs capable of fast power because of safety issues stemming from
charging at above 5 C. Substituting LTO with XNO, and lithium-dendrite formation. This is not an issue for the
NMC with LNMO, demonstrates an increase in energy LNMO/XNO system, which opens up new performance
density for a total of almost 130 WhL-1 at 10 C charge. potential for high-power Li-ion cells at significantly
The model also shows volumetric LNMO/XNO energy higher energy densities.
density of up to 420 WhL-1 at charge rates up to 5 C
(not included in Figure 4). The modelling suggests that, Based on the performance and improved energy density
compared to LTO, the higher gravimetric energy achieved by the LNMO/XNO cell system, it becomes
density and crystal density of XNO, in conjunction with clear that cell manufacturers have an excellent
the higher potential of LNMO compared to NMC622, opportunity to develop differentiated, higher-value cell
increases the cell’s energy density by 55%. In addition, designs.
the cheaper raw material costs of LNMO, compared
to NMC622, reduce the cell cost of an LNMO/XNO
system by 21% compared to the NMC/LTO system.

FIGURE 4.

Figure 4. Modelled output data comparing the energy

density of different cathode/anode pairings that can
achieve 80% retention in charge/discharge at 10 C.

TBM-129 LNMO cathode and XNOTM anode TO CONTENTS 7

5.
APPLICATION OUTLOOK

Today’s battery research and innovations primarily target Systems with LTO (lithium titanate oxide) anode material
passenger electric vehicles (EVs), but such efforts don’t fulfill these criteria, but with low volumetric and
address the user-acceptance criteria for high-duty- gravimetric energy densities.
cycle mission profiles (high-duty- cycle vehicles)
across the areas of cost, performance, safety, and The 3 V LNMO/XNO system provides advantages similar
sustainability. A key battery performance requirement to those of NMC/LTO, NCA/LTO systems, but with up to
for high-duty-cycle vehicles is super-fast charging 55% higher volumetricenergy density (Figure 4). This
(e.g., a 6-minute charge, or a 10 C charge rate), which is superior performance facilitates a wide range of
typically limited by the anode. applications for high-duty- cycle missions - including
those relevant for NMC/LTO, NCA/LTO systems -
Next-gen EV-battery systems, based on silicon/graphite offering greater financial benefits in terms of total cost
(Si/Gr) anodes and NMC/NCA cathodes, are not of ownership and lifecycle costs, and supporting new
expected to support safe fast charging at a rate greater applications where other systems’ low energy density
than 3-4 C while maintaining high (>5000) cycle life. fails to address the user-acceptance criteria, including
This is due to the low voltage of the anode and the high electric ferries, railway rolling stock, automated guided
strain placed on the silicon anode-conversion material. vehicles (AGVs), and mining or construction vehicles.

6.
FINAL MESSAGE

Topsoe and Echion welcome opportunities for

collaboration with cell manufacturers and OEMs
interested in the LNMOXNO cell system presented in
this whitepaper.

Topsoe contact:
Jeppe Winther Hedegaard,
Senior Business Development
Manager
[email protected]
Echion Contact:

Echion Contact:
Harry Geary
Senior Cell Engineer
[email protected]
Harry Geary
Senior Cell Engineer

TBM-129 LNMO cathode and XNOTM anode TO CONTENTS 8

7.
METHODS

Modelling Electrochemical testing

A fully parameterized geometric model was The XNO anode material was cast on an aluminum
implemented in order to describe the LNMO/XNO current collector, with a loading of 7 mg/cm2 and
system and compare its chemistry with that of other an active material:carbon:binder ratio of 92:5:3. The
systems. Values were generated by considering the electrodes were calendared to densities between
separate anode and cathode halfcell capacities, along 2.6-2.8 g/cm3, corresponding to 31-35% porosity, and
with electrode loadings, optimized porosity, and then dried under a vacuum at 120°C for 12 hours. They
N/P ratios from experimental test data in half- and full- were tested in CR2032- type coin cells, with pre-
cells from above. For direct comparisons (i.e., LNMO/ cut lithium disks serving as counter electrodes. The
XNO vs. LNMO/LTO), the anode-mass loading, N/P ratio, formation protocol consisted of 2x0.1 C cycles between
porosity, and cell volume have all been fixed. 1.1–3.0 V.

LNMO cathode material was cast on a carbon-coated

aluminum current collector, with a loading of 8-11 mg/
cm2 and an active material:carbon:binder ratio of 92:4:4.
The electrodes were calendared to densities between
2.6–2.7 g/cm3, corresponding to 31- 35% porosity,
and then dried under a vacuum at 120°C for 12 hours.
Halfcells were assembled in CR2032- type coin cells
with a Celgard separator, 1M LiPF6 in an EC:DEC 1:1
electrolyte, and a pre-cut Li metal anode. Tests were
performed at room temperature, with a formation
protocol of 2x0.1 C cycles between 3.5–5.0 V.

To investigate the individual voltages of both the anode

and cathode while cycling in a full-cell configuration,
3-electrode cell tests were performed in an EL-cell PAT
cell, using lithium as a reference electrode. For the
3-electrode cell test, an NP ratio between 1.1-1.2
was used for balancing the cell, calculated from the
1 C reversible half-cell capacities of LNMO and XNO
(135 mAhg-1 and 200 mAhg-1, respectively). The loading
was kept at a relatively low range in order to facilitate
high-rate charge/discharge capability.

Long-term cycling tests were performed under the

following conditions: CR2032 cells, Celgard H2010
separator, 1M LiPF6 in EC:DEC; temperature at a
constant 25°C; cells cycled at 1 C in charge, with a
CV step and a 1 C discharge. Every 50 cycles, the cells
were checked via a reference cycle of low C-rate at 0.1C

TBM-129 LNMO cathode and XNOTM anode TO CONTENTS 9

Topsoe Echion Technologies
Founded in 1940, Topsoe is a global leader in Spun-out from the University of Cambridge in 2017,
developing solutions for a decarbonized world, Echion is a world-leading developer of advanced
supplying technology, catalysts, and services for lithiumion battery anode materials, whose products
worldwide energy transition. enable cell manufacturers to deliver cost-effective,
fast-charging, high-energy density, and long-life
Our mission is to combat climate change by power cells for a wide range of markets including
helping our partners and customers achieve their automotive, premium consumer electronics, and
decarbonization and emission-reduction targets, grid-storage applications.
including those in challenging sectors: aviation,
shipping, and production of crucial raw materials. Echion provides materials and battery-cell
manufacturers with packages of protected
From low-carbon or zero-carbon chemicals to intellectual property, customization options,
renewable fuels and plastic upcycling, we are materials synthesis, and cellintegration
uniquely positioned to aid humanity in realizing a know-how for different end-user markets.
sustainable future.
XNO is a trademark of Echion Technologies.
Topsoe is headquartered in Denmark, with 2,400 To learn more, visit echiontech.com
employees serving customers all around the globe.
To learn more, visit topsoe.com

Get in touch today

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Topsoe A/S
Haldor Topsøes Allé 1
2800 Kongens Lyngby
Denmark

Tel. +45 45 27 20 00
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0344.2023/Rev.1