All Solid Battery Including A Solid Electrolyte And A Layer Of Polymer Material
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 a layer including at least one solid
electrolyte material on at least one layer obtained in step a) and/or b); d) depositing a layer of a cross-linked polymer material comprising ion groupings with a thickness of less than 10 µm, preferably less than 5 µm, and more preferably less than 2 µm: either on the layer of
anode material coated with a layer of solid electrolyte material and/or on the layer of cathode material optionally coated with a layer of solid electrolyte material, or on the layer of cathode material coated with a layer of solid electrolyte material and/or on the layer of anode material optionally coated with a layer of solid electrolyte material; e) consecutively stacking, face-toface, a layer of anode material obtained in steps a), c) or d) with a layer of cathode material obtained in steps b), c) or d), with the understanding that the stack includes at least one layer of solid electrolyte material obtained in step c) and at least one layer of cross-linked polymer material obtained in step d); f) thermally treating and/or a mechanically compressing of the stack obtained in step e) in order to obtain an all-solid thin-film battery.
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Notices, Deadlines & Correspondence
6 RUE DES AULNES, CHAMPAGNE-AU-MONT-D'OR, FRANCE-69410
Inventors
1. GABEN, Fabien
5 Montee du Clair, Dardily, France, 69570
Specification
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.
All-solid thin-layer Li-ion batteries having a
planar architecture, i.e. which are essentially comprised
of a set of three layers forming a basic battery cell: an
anode layer and a cathode layer separated by an
electrolyte layer are also known.
They use metallic lithium anodes and lithium
phosphorus oxynitride films as the electrolyte. However,
significant variations in volume of the lithium anode in
charging and discharging steps makes it extremely
difficult to properly encapsulate the battery without the
risk of loss of tightness of the encapsulation.
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More recently, new all-solid battery architectures
consisting of a stack of thin layers have been proposed.
These batteries consist of a rigid and monobloc assembly
of basic cells connected in parallel. These batteries use
dimensionally stable anodes to ensure the efficacy of the
encapsulation, and enable three-dimensional structures to
be produced, with better surface energy densities than
the planar architectures. Such batteries are described in
documents WO 2013/064779 A1 or WO 2012/064777 A1. The
batteries described in these documents do not contain
organic solvent-based liquid electrolyte, their structure
consists of all-solid thin layers, without porosity in
the electrode layers in order to ensure good properties
of stability of the battery over time. The process for
producing these batteries, also described in documents
WO 2013/064779 A1 or WO 2012/064777 A1, has numerous
advantages because it makes it possible to produce
multilayer, thin-layer and therefore relatively nonresistant assemblies, enabling performance in terms of
power to be preserved.
However, in some cases, the process of producing
such batteries may have some limits according to the
materials used, in particular for the electrolyte. In
fact, ionic conductive glasses may be difficult to
implement. For example, solid electrolytes such as LiPON
or lithiated borates have a relatively low glass
transition temperature, generally between around 250 and
300°C: thus, during the step of assembly of the battery
by pressurized annealing of the different layers, the
electrolyte materials may partially crystallize, which
may modify their ionic conduction property. Similarly,
when the solid lithium phosphorus-based electrolyte is
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used, it may be beneficial to differentiate the chemical
compositions of the electrolytes in contact with the
anodes and cathodes in order to optimize the performance
of the electrolytes.
However, the use of two lithium phosphorus-based
electrolyte formulations deposited on each of the faces
of the electrodes may lead to the appearance of new
phases at the interface between the two electrolyte
layers to be assembled, and may therefore modify the
conduction properties.
Similarly, solid Li7La3Zr2O12 (called LLZO)
electrolytes are good ionic conductors and are very
stable in contact with anodes and cathodes, but their
highly refractory character makes it sometimes difficult
to weld, at low temperature, the electrodes to one
another via the electrolyte layer without causing an
interdiffusion phenomenon at the interfaces with the
electrodes.
A first objective of the present invention is to
propose a process for producing all-solid thin-layer
batteries that do not lead to the appearance of phases at
the interface between the two electrolyte layers to be
assembled.
Another objective of the present invention is to
propose a process for producing a battery at low
temperature without causing interdiffusion phenomena at
the interfaces with the electrodes.
Another objective of the invention is to produce
thin-layer batteries capable of being implemented by on
an industrial level in a relatively simple manner.
Objects of the invention
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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
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 at least one 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;
d) a layer of a cross-linked polymer material
comprising ionic groups having a thickness of less than
10 µm, preferably less than 5 µm and even more preferably
less than 2 µm is deposited:
- on the anode material layer coated with a solid
electrolyte material layer and/or on the cathode material
layer coated or not with a solid electrolyte material
layer;
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- or on the cathode material layer coated with a
solid electrolyte material layer and/or on the anode
material layer coated or not with a solid electrolyte
material layer;
e) an anode material layer obtained in step a), c)
or d) is stacked face to face in series with a cathode
material layer obtained in step b), c) or d) with the
understanding that the stack includes at least one solid
electrolyte material layer obtained in step c) and at
least one cross-linked polymer material layer obtained in
step d);
f) a heat treatment and/or a mechanical compression
of the stack obtained in step e) is carried out in order
to obtain an all-solid thin-layer battery.
The cross-linked polymer is preferably chosen from
polymethyl methacrylates, polyamines, polyimides or
polysiloxanes.
Preferably, the ionic groups of the polymer material
are chosen from the following cations: imidazolium,
pyrazolium, tetrazolium, pyridinium, pyrrolidinium, such
as n-propyl-n-methylpyrrolidinium (also called PYR13) or
n-butyl-n-methylpyrrolidinium (also called PYR14),
ammonium, phosphonium or sulfonium; and/or from the
following anions: bis(trifluoromethane)sulfonimide,
bis(fluorosulfonyl)imide, or n-(nonafluorobutanesulfonyl)-n-(trifluoromethanesulfonyl)-imide.
In a particular embodiment, the cross-linked polymer
material is obtained by a step of polymerization of a
mixture of monomers and/or oligomers and/or pre-polymers
including one or more thermally or photochemically
polymerizable groups, said mixture of monomers and/or
oligomers and/or pre-polymers including one or more
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reactive groups enabling said ionic groups to be grafted.
Preferably, the thermal and/or photochemical
polymerization is performed directly on the anode,
cathode and/or electrolyte layer(s).
Advantageously, the deposition of the cross-linked
polymer material comprising ionic groups is performed
using at least one of the following techniques: dipcoating, spin-coating, roll coating, doctor blade,
electrospraying or electrophoresis.
The thickness of the polymer material layer is less
than 10 µm, preferably less than 5 µm and even more
preferably less than 2 µm. Advantageously, the thickness
of the polymer material layer is between 0.5 and 1 µm.
The solid anode, cathode and electrolyte layers are
deposited using at least one of 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.
Preferably, the anode, cathode and electrolyte
layers are deposited by electrospraying, electrophoresis,
using an aerosol, or by dipping, and are preferably all
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deposited by electrophoresis.
In a particular embodiment, the layers of anode
and/or cathode material also include electrically
conductive materials, and in particular graphite, and/or
nanoparticles of lithium ion conductive materials, of the
type used to produce electrolyte films, or cross-linked
solid polymer materials comprising ionic groups.
Preferably, the anode and/or cathode and/or
electrolyte layers are produced by a deposition of
nanoparticles, respectively, of anode, cathode or
electrolyte material using at least one of the following
techniques: electrospraying, electrophoresis, aerosol
deposition, and dipping. More specifically, the layers of
anode, cathode and electrolyte material nanoparticles are
all deposited by electrophoresis.
According to the invention, the heat treatment is
performed at a temperature of between 50°C and 300°C,
preferably between 100°C and 200°C, and/or the mechanical
compression of the layers to be assembled is performed at
a pressure of between 10 and 100 MPa, and preferably
between 20 and 50 MPa.
The anode material layer a) is produced from a
material chosen from:
(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,
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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