Solid State Battery Including An Electrolyte Made Of A Cross Linked Solid Polymer Material
Abstract:
The invention relates to a method for manufacturing a thin-layer solid-state 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 at least one layer obtained in step a) and/or b) a layer including at least one solid electrolyte material having a thickness smaller than 10 µm, preferably smaller than 5 µm, and even more preferably smaller 2 µm, the solid electrolyte material including a cross-linked solid polymer material comprising ion groupings; d) consecutively stacking the following face-to-face: either a layer of anode material coated with a layer of solid 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 solid 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) performing a thermal treatment and/or a mechanical compression of the stack obtained in step d) in order to obtain a thin-layer solid-state 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
5 batteries.
Prior art
Batteries including electrolytes formed either by a
salt dissolved in a dry polymer or by a polymer swollen
10 or gelled by a solution of a salt in a mixture of organic
aprotic polar solvents are known. Typically, the
production of the electrolyte consists in placing a
polymer, a salt and a mixture of solvents forming the
polymer electrolyte in solution, then, after having
15 deposited the mixture in the form of a film, the solvent
is removed under atmospheric or reduced pressure without
removing the solvents forming the polymer electrolyte.
Document WO 98 / 35 397 A1 describes a battery including
an electrolyte formed by a dried electrolyte solution
20 including a thermoplastic polyimide that is amorphous and
soluble in an organic solvent, and a lithium salt.
However, the use of organic solvent does not make it
possible to guarantee the safety and lifetime of the
battery by protecting it from risks of short circuit and
25 ignition of solvent.
All-solid batteries including solid electrolytes
produced from polymer material based on polyethylene
oxide (PEO) or polypropylene oxide (PPO) are also known.
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However, these types of electrolytes have a relatively
low ionic conductivity at ambient temperature
(approximately 10-7 S/cm). Document US 5 407 593 teaches
that the transport of ions in a polymer electrolyte
5 passes through the amorphous region of a polymer matrix.
Thus, the ionic conductivity of a polymer electrolyte may
be increased by reducing the crystalline region and by
increasing the amorphous region of the polymer. In
addition, it is possible by modifying the glass
10 transition temperature of the polymer, by removing the
crystalline zones and by using lower molecular masses, to
increase ionic conduction. However, these modifications
to the polymer material often create significant
degradation of the mechanical properties of the
15 electrolyte.
In addition, it has been demonstrated that crosslinking
of the conductive polymer may increase the
solidity of the films, but this results in a reduction in
conductivity. For example, the article of P.M. Blonsky
20 and D.F. Shriver, J. Am. Chem. Soc. 1984, 106, pages
6854-6855 describes a polymer of the poly(bis(methoxy
ethoxy)phosphazene) type including short chains of
polyethylene oxide of which the ionic conductivity at
25°C exceeds 10-5 S/cm. However, the electrochemical
25 stability of the cross-linked solid polymer material as
well as its mechanical properties are limited.
The present invention is intended to produce an allsolid
battery including a solid electrolyte made of a
cross-linked polymer material, having good mechanical
30 resistance and having an ionic conductivity superior to
that of solid electrolytes made of a cross-linked polymer
material known from the prior art.
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Another objective of the invention is to produce
thin-layer batteries by a process capable of being
implemented at an industrial level in a relatively simple
manner.
5
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:
10 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
15 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
20 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,
25 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 having a thickness of less than 10 μm,
30 preferably less than 5 μm and even more preferably less
than 2 μm (referred to here as “electrolyte material
layer”) is deposited, the solid electrolyte material
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including a cross-linked solid polymer material
comprising ionic groups;
d) the following are stacked face to face:
- an anode material layer coated with a solid
5 electrolyte material layer obtained in step c) with a
cathode material layer coated or not with a solid
electrolyte material layer obtained in step c);
- or a cathode material layer coated with a solid
electrolyte material layer obtained in step c) with an
10 anode material layer coated or not with a solid
electrolyte material layer obtained in step c);
e) a heat treatment and/or a mechanical compression
of the stack obtained in step d) is performed in order to
obtain an all-solid thin-layer battery.
15 Preferably, the solid cross-linked polymer material
is chosen from polymethyl methacrylates, polyamines,
polyimides or polysiloxanes.
Preferably, the ionic groups of the polymer material
are chosen from the following cations: imidazolium,
20 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,
25 bis(fluorosulfonyl)imide, or n-(nonafluorobutanesulfonyl)-
n-(trifluoromethanesulfonyl)-imide.
In a particular embodiment of the process according
to the invention, the solid cross-linked polymer material
is obtained by a step of polymerization of a mixture of
30 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
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pre-polymers including one or more reactive groups
enabling said ionic groups to be grafted, then drying of
the cross-linked polymer material obtained.
Advantageously, the thermal and/or photochemical
5 polymerization is performed directly on the anode and/or
cathode layer(s).
The cross-linked polymer material comprising ionic
groups deposited in step c) is performed by at least one
of the following techniques: dip-coating, spin-coating,
10 roll coating, doctor blade, electrospraying or
electrophoresis.
The thickness of the electrolyte layer c) is less
than 10 μm, preferably less than 5 μm and even more
preferably less than 2 μm. Advantageously, the thickness
15 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
20 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
25 (AA-CVD);
(iii) electrospraying;
(iv) electrophoresis;
(v) aerosol deposition;
(vi) sol-gel;
30 (vii) dipping, more specifically dip-coating, spincoating
or the Langmuir-Blodgett process.
Preferably, the anode, cathode and electrolyte
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layers are deposited by electrospraying, electrophoresis,
using an aerosol, or by dipping, and are preferably all
deposited by electrophoresis.
Advantageously, the layers of anode and/or cathode
5 material also include electrically conductive materials,
and in particular graphite, and/or lithium ion conductive
materials, of the type used to produce electrolyte films.
In a preferred embodiment, the anode and/or cathode
and/or electrolyte layers are produced by a deposition of
10 nanoparticles, respectively, of anode, cathode or
electrolyte material using at least one of the following
techniques: electrospraying, electrophoresis, aerosol
deposition, and dipping.
Preferably, the layers of anode, cathode and
15 electrolyte material are all deposited by
electrophoresis.
Advantageously, the heat treatment is performed at a
temperature of between 50°C and 100°C, preferably between
100°C and 200°C, and/or the mechanical compression of the
20 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:
25 (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