Process For Producing An All Solid Thin Layer Battery Including A Lithium Phosphate Solid Electrolyte
Abstract:
The invention relates to a method for manufacturing an all-solid thin-film battery including the following consecutive steps: a) depositing a layer including at least one anode material on the conductive substrate thereof; b) depositing a layer including at least one cathode material on the conductive substrate thereof; c) depositing on the layer obtained in step a) and/or b) a layer including at least one solid electrolyte material selected among: Li3(Sc2-xMx)(P04)3 wherein M = Al or Y and 0 ≤ x ≤ 1; or Li1+xMx(Sc)2-x(P04)3 wherein M = Al, Y, Ga or a mixture of the three compounds and 0 ≤ x ≤ 0.8; or Li1+xMx(Ga1-yScy)2-x(P04)3 wherein 0 ≤ x ≤ 0.8; 0 ≤ y ≤ 1 and M = Al or Y; or a mixture of the two compounds; or Li1+xMx(Ga)2-x(P04)3 wherein M = Al, Y or a mixture of the two compounds and 0 ≤ x ≤ 0.8; or Li3+y(Sc2-xMxQyP3-yO12, wherein M = Al and/or Y and Q = Si and/or Se, 0 ≤ x ≤ 0.8 and 0 ≤ y ≤ 1; or Li1+x+yMxSc2-xQyP3-yO12, wherein M = Al, Y, Ga or a mixture of the three compounds and Q = Si and/or Se, 0 ≤ x ≤ 0.8 and 0 ≤ y ≤ 1; or Li1+x+y+zMx(Gai-yScy)2-xQzP3-zOi2 wherein 0 ≤ x ≤ 0.8; 0 < y < 1; 0 ≤ z ≤ 0.6 wherein M = Al or Y or a mixture of the two compounds and Q= Si and/or Se; Li1+xNxM2-xP3012, wherein 0 ≤ x ≤ 1 and N = Cr and/or V, M = Se, Sn, Zr, Hf, Se or Si, or a mixture of these compounds; d) consecutively stacking, face-to-face: either a layer of anode material coated with a layer of electrolyte material obtained in step c) with a layer of cathode material optionally coated with a layer of solid electrolyte material obtained in step c), or a layer of cathode material coated with a layer of electrolyte material obtained in step c) with a layer of anode material optionally coated with a layer of solid electrolyte material obtained in step c); and e) thermally treating and/or a mechanically compressing the stack obtained in step d) in order to obtain an all-solid thin-film battery.
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Notices, Deadlines & Correspondence
Technical field
This invention relates to the field of batteries and
in particular lithium-ion batteries. It relates more
specifically to all-solid lithium ion batteries (“Li-ion
batteries”) and a novel process for producing such
batteries.
Prior art
Modes of producing lithium-ion batteries (“Li-ion
batteries”) presented in numerous articles and patents
are known; the work “Advances in Lithium-Ion Batteries”
(ed. W. van Schalkwijk and B. Scrosati), published in
2002 (Kluever Academic / Plenum Publishers) provides a
good review of the situation. The electrodes of Li-ion
batteries may be produced by means of printing or
deposition techniques known to a person skilled in the
art, and in particular by roll-coating, doctor blade or
tape casting.
There are various architectures and chemical
compositions of electrodes enabling Li-ion batteries to
be produced. Recently, Li-ion batteries formed by allsolid
thin layers have appeared. These batteries
generally have a planar architecture, that is, they are
essentially formed by a set of three layers forming a
basic battery cell: an anode layer and a cathode layer
separated by an electrolyte layer. More recently, Li-ion
batteries with three-dimensional structures have been
produced using new processes. Such processes are in
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particular disclosed in documents WO 2013/064 779 A1 or
WO 2012/064 777 A1. In these documents, the production of
anode, solid electrolyte and cathode layers is performed
by electrophoresis. The batteries obtained by this
process have a high power density; they also have a high
energy density (around twice that of known lithium-ion
batteries) due to the very low porosity level and the low
thickness of the electrolyte films. In addition, the
batteries obtained by these processes do not contain
metallic lithium or organic electrolytes. Thus, they may
be resistant when subjected to high temperatures.
Finally, when they are produced in the form of a
“microbattery”-type electronic component, they may then
be tested before being welded to circuits, without the
risk of damage, in particular when the batteries are in a
partially charged or discharged state.
However, the performance of these all-solid
batteries may be variable. Obtaining sustainable
performance over time is dependent not only on the choice
of the electrolytes and production parameters but also
the overall architecture of the battery. For example,
depending on the chemical composition and nature of the
electrolyte film, internal resistance may appear at the
interfaces with the electrodes.
Moreover, certain electrolytes disclosed in these
documents are based on sulfides, which are stable within
a broad potential range, but which have a tendency to
create strong resistance to the transfer of charges at
their interfaces with the electrodes. Furthermore, solid
sulfide-based electrolytes are extremely hygroscopic,
which may make it difficult to implement them on an
industrial scale and may cause particular sensitivity to
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aging.
In addition, these documents disclose ionic
conductive glass-based electrolytes, such as LiPON or
lithiated borate. However, these have a relatively low
glass transition temperature and are therefore capable of
partially crystallizing during assembly of the battery by
heat treatment; this causes their ionic conduction
properties to deteriorate. Finally, these components
remain relatively sensitive in contact with the
atmosphere, making them difficult to implement on an
industrial level.
Electrolytes containing lithiated phosphate-based
materials are also known, the latter being stable in
contact with the atmosphere and stable at high potential.
However, these electrolytes are usually unstable in
contact with anodes in lithium. The instability of these
electrolytes in contact with anodes is essentially due to
the presence of metallic elements capable of having
multiple oxidation states that, when in contact with the
low-potential anodes, will be reduced and change
oxidation states. This chemical modification gradually
renders the electrolyte electrically conductive, which
degrades the performance of the battery.
This family of electrolytes includes Li1+xAlxTi2-
x(PO4)3 (called LATP) in which a titanium reduction may
appear at 2.4 V, and Li1+xAlxGe2-x(PO4)3 (called LAGP) in
which a germanium reduction may appear at 1.8 V.
Aside from the electrochemical degradation of the
electrolytes and other aging phenomena associated with
the sensitivity to air of certain constituents of the Liion
battery cell, the degradation of performance of Liion
batteries may also come from the cathode. In fact,
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lithium insertion materials used to produce cathodes have
reversible behavior only in a certain potential range.
When the level of lithium inserted decreases below a
certain threshold, crystallographic modifications may
appear, causing irreversible losses in performance of the
cathode materials. However, conventional Li-ion batteries
as well as thin-layer Li-ion batteries using metallic
lithium anodes have lithium ion storage capacities (at
the anode level) greater than that at the cathode. In
fact, in the case of batteries with metallic lithium
anodes, the capacity of the anode is practically
unlimited, and the lithium may be deposited onto the
anode as it arrives. For standard Li-ion batteries using
liquid electrolytes with lithium salts, an anode capacity
lower than that of the cathode may lead to the formation
of metallic lithium precipitates in the battery during
charging. These precipitates form when the cathode
produces lithium ions in excess of what the anode is
capable of accepting. As the formation of metallic
lithium precipitates in a battery cell is capable of
causing a risk of thermal runaway, it is essential to
ensure that the anodes have sufficient capacities to
prevent the appearance of such a risk.
Although it is more of a safety measure, this
architecture may in some cases lead to an extraction of
too many lithium ions from the cathode, in particular
during high-power cycling phases on charged batteries.
This may irreversibly deteriorate the insertion capacity
of the battery and lead to its aging.
In addition, the aging of the battery and the loss
of its capacity may also result from the precipitation of
lithium ions in the porosities of the electrodes, thereby
5
reducing the quantity of lithium ions available for
operation of the battery, as well as the loss of contacts
between the electrode particles.
A first objective of the present invention is to
produce all-solid thin-layer batteries, in which the
materials used for the electrolyte layers are stable in
contact with anodes and cathodes in order to improve the
operation and lifetime of said batteries.
Yet another objective is to produce all-solid thinlayer
batteries in which the materials used for the
electrolyte layers do not enable the formation of
metallic lithium precipitates, or internal resistance at
the interfaces with the electrodes.
Another objective of the invention is to produce
thin-layer batteries by a process capable of being
implemented on an industrial level in a relatively simple
manner.
Objects of the invention
A first object of the invention concerns a process
for producing an all-solid thin-layer battery including
the following series of steps:
a) a layer including at least one anode material
(referred to here as “anode material layer”) is deposited
on its conductive substrate, preferably selected from the
group formed by a metal sheet, a metal strip, a
metallized insulating sheet, a metallized insulating
strip, a metallized insulating film, said conductive
substrates, or conductive elements thereof, capable of
serving as an anode current collector;
b) a layer including at least one cathode material
(referred to here as “cathode material layer”) is
6
deposited on its conductive substrate, preferably
selected from the group formed by a metal sheet, a metal
strip, a metallized insulating sheet, a metallized
insulating strip, a metallized insulating film, said
conductive substrates, or conductive elements thereof,
capable of serving as a cathode current collector, with
the understanding that steps a) and b) can be reversed;
c) on the layer obtained in step a) and/or b), a
layer including at least one solid electrolyte material
(referred to here as “electrolyte material layer”) is
deposited, chosen from:
- Li3(Sc2-xMx)(PO4)3 with M = Al or Y and 0 ≤ x ≤ 1;
or
- Li1+xMx(Sc)2-x(PO4)3 with M = Al, Y, Ga or a mixture
of the three compounds and 0 ≤ x ≤ 0.8; or
- Li1+xMx(Ga1-yScy)2-x(PO4)3 with 0 ≤ x ≤ 0.8; 0 ≤ y ≤ 1
and M = Al or Y; or a mixture of the two compounds; or
- Li1+xMx(Ga)2-x(PO4)3 with M = Al, Y; or a mixture of
the two compounds and 0 ≤ x ≤ 0.8; or
- Li3+y(Sc2-xMx)QyP3-yO12 with M = Al and/or Y and Q =
Si and/or Se, 0 ≤ x ≤ 0.8 and 0 ≤ y ≤ 1; or
- Li1+x+yMxSc2-xQyP3-yO12 with M = Al, Y, Ga or a mixture
of the three compounds and Q = Si and/or Se, 0 ≤ x ≤ 0.8
and 0 ≤ y ≤ 1; or
- Li1+x+y+zMx(Ga1-yScy)2-xQzP3-zO12 with 0 ≤ x ≤ 0.8; 0 ≤ y
≤ 1; 0 ≤ z ≤ 0.6 with M = Al or Y or a mixture of the two
compounds and Q = Si and/or Se;
- Li1+xNxM2-xP3O12 with 0 ≤ x ≤ 1 and N = Cr and/or V,
M = Sc, Sn, Zr, Hf, Se or Si, or a mixture of these
compounds;
d) the following are stacked, layer upon layer, in
series:
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- a layer including at least one anode material
coated with a layer including at least one electrolyte
material obtained in step c) with a layer including at
least one cathode material coated or not with a layer
including at least one electrolyte material obtained in
step c);
- or a layer including at least one cathode material
coated with a layer including at least one electrolyte
material obtained in step c) with a layer including at
least one anode material coated or not with a layer
including at least one electrolyte material obtained in
step c);
e) a heat treatment and/or a mechanical compression
of the stack obtained in step d) is carried out in order
to obtain an all-solid thin-layer battery.
In a particular embodiment of the process according
to the invention, when a layer of electrolyte material is
deposited on the layer obtained in step a), a layer of at
least one material chosen from the following is
optionally deposited on the layer obtained in step b):
- Li3(Sc2-xMx)(PO4)3 with M = Al or Y and 0 ≤ x ≤ 1;
or
- Li1+xMx(Sc)2-x(PO4)3 with M = Al, Y, Ga or a mixture
of two or three compounds and 0 ≤ x ≤ 0.8; or
- Li1+xMx(Ga1-yScy)2-x(PO4)3 with 0 ≤ x ≤ 0.8; 0 ≤ y ≤ 1
and M = Al or Y; or a mixture of the two compounds; or
- Li1+xAlxTi2-x(PO4)3 with 0 ≤ x ≤ 1; or
- Li1+xAlxGe2-x(PO4)3 with 0 ≤ x ≤ 1; or
- Li1+x+zMx(Ge1-yTiy)2-xSizP3-zO12 with 0 ≤ x ≤ 0.8; 0 ≤ y
≤ 1; 0 ≤ z ≤ 0.6 and M = Al, Ga or Y or a mixture of two
or three of these compounds; or
- Li3+y(Sc2-xMx)QyP3-yO12, with M = Al and/or Y and Q =
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Si and/or Se, 0 ≤ x ≤ 0.8 and 0 ≤ y ≤ 1; or
- Li1+x+yMxSc2-xQyP3-yO12 with M = Al, Y, Ga or a mixture
of the three compounds and Q = Si and/or Se, 0 ≤ x ≤ 0.8
and 0 ≤ y ≤ 1; or
- Li1+x+y+zMx(Ga1-yScy)2-xQzP3-zO12 with 0 ≤ x ≤ 0.8; 0 ≤ y
≤ 1; or 0 ≤ z ≤ 0.6 with M = Al or Y or a mixture of the
two compounds and Q = Si and/or Se;
- Li1+xNxM2-xP3O12 with 0 ≤ x ≤ 1 and N = Cr and/or V,
M = Sc, Sn, Zr, Hf, Se or Si or a mixture of these
compounds.
According to the invention, the layers including at
least one anode material, at least one cathode material
and at least one solid electrolyte material are deposited
by one or more techniques selected from the following
techniques:
(i) physical vapor deposition (PVD), and more
specifically by vacuum evaporation, laser ablation, ion
beam, or cathode sputtering;
(ii) chemical vapor deposition (CVD), and more
specifically plasma-enhanced chemical vapor deposition
(PECVD), laser-assisted chemical vapor deposition
(LACVD), or aerosol-assisted chemical vapor deposition
(AA-CVD);
(iii) electrospraying;
(iv) electrophoresis;
(v) aerosol deposition;
(vi) sol-gel;
(vii) dipping, more specifically dip-coating, spincoating
or the Langmuir-Blodgett process.
Advantageously, said anode and/or cathode and/or
electrolyte layers are produced by deposition of
nanoparticles, respectively, of anode, cathode or
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electrolyte material, by one or more techniques selected
from the following techniques: electrospraying,
electrophoresis, aerosol deposition, and dipping.
Preferably, the anode, cathode and electrolyte
layers are all deposited by electrophoresis, preferably
from nanoparticles of cathode material(s), electrode
material(s) and anode material(s).
According to the invention, the anode material layer
a) is produced from material chosen from the following:
(i) tin oxynitrides (typical formula SnOxNy);
(ii) lithiated iron phosphate (typical formula
LiFePO4);
(iii) mixed silicon and tin oxynitrides (typical
formula SiaSnbOyNz with a>0, b>0, a+b≤2, 00,
b>0, a+b≤2, 00, b>0, a+b>0, a+b≤2,
00, b>0, a+b≤2, 00, b>0, a+b≤2, 00,
b>0, a+b≤2, 00, b>0, a+b>0, a+b≤2,
00, b>0, a+b≤2, 00, b>0, a+b≤2, 00, b>0,
a+b≤2, 00, b>0, a+b>0, a+b≤2, 00, b>0, a+b≤2, 0
Documents
Orders
Section
Controller
Decision Date
Application Documents
#
Name
Date
1
201617044320-IntimationOfGrant07-04-2022.pdf
2022-04-07
1
Form 5 [26-12-2016(online)].pdf
2016-12-26
2
201617044320-PatentCertificate07-04-2022.pdf
2022-04-07
2
Form 3 [26-12-2016(online)].pdf
2016-12-26
3
Form 1 [26-12-2016(online)].pdf
2016-12-26
3
201617044320-Response to office action [15-03-2022(online)].pdf
2022-03-15
4
Drawing [26-12-2016(online)].pdf
2016-12-26
4
201617044320-Written submissions and relevant documents [23-12-2021(online)].pdf