Process For Manufacturing A Monolithic All Solid State Battery
Abstract:
The invention relates to a process for manufacturing all solid state batteries said batteries comprising at least one dense layer containing anode materials ("anode layer") at least one dense layer containing solid electrolyte materials ("electrolyte layer") and at least one dense layer containing cathode materials ("cathode layer") in order to obtain an all solid state battery consisting of an assembly of a plurality of elementary cells.
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Notices, Deadlines & Correspondence
Field of the invention
This invention relates to the field of batteries and
in particular lithium ion batteries. It relates more
specifically to all-solid-state lithium ion batteries,
and a novel process for manufacturing such batteries.
5
Prior art
The modes for manufacturing lithium ion batteries
("Li-ion batteries") are presented in many articles and
patents, and the work "Advances in Lithium-Ion Batteries"
10 (ed. W. van Schalkwijk and B. Scrosati), published in
2002 (Kluever Academic / Plenum Publishers) provides a
good assessment of them. The electrodes of Li-ion
batteries can be produced by means of printing or
deposition techniques known to a person skilled in the
15 art (in particular: roll coating, doctor blade, tape
casting). These techniques make it possible to produce
depositions having a thickness of between 50 and 400 μm.
Depending on the thickness of the depositions, their
porosities and the size of the active particles, the
20 power and energy of the battery may be modulated.
More recently, other Li-ion battery architectures
have appeared. These are primarily all-solid-state thinfilm
microbatteries. These microbatteries have a planar
architecture, that is, they consist essentially of an
25 assembly of three layers forming an elementary battery
cell: an anode layer and a cathode layer separated by an
electrolyte layer. These batteries are said to be “allsolid-
state” because the two electrodes (anode and
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WO 2014/131997 2 PCT/FR2014/050424
cathode) and the electrolyte are made of non-porous solid
materials. These batteries have an important advantage
owing to their superior performance to those of
conventional electrolyte-based batteries including
5 lithium salts dissolved in an aprotic solvent (liquid or
gel electrolyte). The absence of liquid electrolyte
considerably reduces the risks of internal short-circuit
and thermal runaway in the battery.
Different vacuum deposition techniques have been
10 used to produce thin-film microbatteries. In particular,
physical vapor deposition (PVD) is the technique most
commonly used at present to produce these thin-film
microbatteries. This technique makes it possible to
produce high-quality electrode and electrolyte layers
15 without porosity. These layers are generally thin
(generally less than 5 μm) so as not to cause excessive
power loss associated with an increase in the electrode
thicknesses.
Numerous approaches have been proposed in order to
20 produce all-solid-state batteries. In general, these
approaches are based only on high-pressure mechanical
compaction of electrode and electrolyte material powders
(Journal of Power Sources, 2009, 189, 145-148 H. Kitaura).
Nevertheless, the electrode and electrolyte layers
25 obtained are porous and the adhesion between them is not
optimal, so that the internal resistance of said
batteries is too high and does not enable a high power to
be generated.
To improve the performance of all-solid-state
30 batteries, a number of sintering techniques have been
used, either using thermal treatments (Journal of Power
Sources, 2007, 174, K. Nagata) or pulsed current
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WO 2014/131997 3 PCT/FR2014/050424
(Material Research Bulletin, 2008, X. Xu). However,
sintering leads to significant shrinkage and/or the use
of high temperature. Consequently, it is not possible to
perform the all-solid-state electrode deposition on
5 conductive metal substrates, and more specifically
aluminum substrates. Indeed, an excessively high
temperature would oxidize or significantly deteriorate
the metal substrate. Moreover, the layer deposited on the
substrate would lead to the appearance of cracks during
10 sintering. These disadvantages require current collectors
to be deposited on the ends of the battery cell formed by
a cathode/electrolyte/anode stack. Consequently, the
restriction associated with the deposition of current
collectors does not make it possible to produce a three15
dimensional battery assembly, all-solid-state, monolithic,
consisting of a plurality of elementary cells.
This invention is therefore intended for producing
an all-solid-state monolithic Li-ion battery, the
monolithic body consisting of a plurality of elementary
20 cells, by producing dense electrode deposits directly on
the two faces of a substrate acting as a battery current
collector, and by depositing an all-solid-state dense
electrolyte layer on at least one of the dense electrode
deposits obtained.
25
Subject matter of the invention
This invention relates to a process for producing
all-solid-state batteries, said batteries including at
least one dense layer containing anode materials ("anode
30 layer"), at least one dense layer containing solid
electrolyte materials ("electrolyte layer"), and at least
one dense layer containing cathode materials ("cathode
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WO 2014/131997 4 PCT/FR2014/050424
layer"), in order to obtain an all-solid-state battery
consisting of an assembly of a plurality of elementary
cells, the process including the following steps:
a) a dense anode layer and a dense cathode layer are
5 each deposited on their respective conductive substrates,
said conductive substrates being capable of serving as an
anode and cathode current collector, respectively;
b) a dense solid electrolyte layer is deposited on
at least one of the two layers obtained in step a);
10 c) a layer containing at least one Ms bonding
material is deposited on at least one of the layers
obtained in step a) and /or b); with the understanding
that the depositions of the layers of step a), b) and c)
are not all performed by electrophoresis;
15 d) the layer obtained in step c) is stacked face-toface
with a layer obtained in step a), b) or c);
e) a thermal treatment and/or mechanical compression
promoting contact between said two layers stacked faceto-
face is performed in order to obtain an all-solid20
state assembly of elementary cells, capable of
functioning as a battery.
Preferably, the deposition of the anode and cathode
layer is performed on the two faces of their respective
conductive substrates.
25 In a preferred embodiment, the thermal treatment
performed in step e) is performed at a temperature TR
which, preferably, does not exceed 0.7 times the melting
or decomposition temperature (expressed in C), and more
preferably does not exceed 0.5 times (and even more
30 preferably does not exceed 0.3 times) the melting or
decomposition temperature (expressed in C) of the at
least one most fusible Ms bonding material subjected to
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WO 2014/131997 5 PCT/FR2014/050424
said thermal treatment step. Similarly, the mechanical
compression of the assembly obtained in step e) is
performed at a pressure of between 10 and 100 MPa,
preferably between 10 and 50 MPa.
5 The deposition of the layers of step a), b) and c)
are performed by vapor phase and/or by wet deposition,
and mores specifically at least one of the following
techniques:
i) physical vapor deposition (PVD), and more
10 specifically vacuum evaporation, laser ablation, ion beam,
cathode sputtering;
ii) chemical vapor deposition (CVD) and more
specifically plasma-enhanced chemical vapor deposition
(PECVD), laser-assisted chemical vapor deposition (LACVD),
15 or aerosol-assisted chemical vapor deposition (AA-CVD);
iii) electrospraying;
iv) aerosol deposition;
v) electrophoresis;
vi) sol-gel;
20 vii) dipping, more specifically dip-coating, spincoating
or the Langmuir-Blodgett process.
The Ms bonding material is preferably selected from
one or more of the following materials:
a) oxide-based materials chosen from Li3.6Ge0.6V0.4O4;
25 Li2O-Nb2O5; LiSiO4; Li2O; Li14Zn(GeO4)4; Li6Zr2O7; Li8ZrO6;
Li0.35La0.55TiO3; Li0.5La0.5TiO3; Li7La3Zr2O12; Li5+xLa3(Zrx,A2-
x)O12 with A=Sc, Ti, V, Y, Nb, Hf, Ta, Al, Si, Ga, Ge, Sn
and 1.4 ≤ x ≤ 2;
b) nitride- or oxynitride-based materials chosen
30 from Li3N; Li3PO4-xN2x/3, Li4SiO4-xN2x/3, Li4GeO4-xN2x/3 with 0 <
x 4 or Li3BO3-xN2x/3 with 0 < x < 3; lithium and phosphorus
oxynitride-based materials (called LiPON) that may also
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WO 2014/131997 6 PCT/FR2014/050424
contain silicon (called LiSiPON), boron (called LiPONB),
sulfur (called LiPONS), zirconium or aluminum (called
LiPAON) or a combination of aluminum, boron, sulfur
and/or silicon; the lithium and boron oxynitride-based
5 materials (called LiBON) that may also contain silicon
(called LiSiBON), sulfur (called (LIBONS) or aluminum
(called LiBAON) or a combination of aluminum, sulfur and
silicon; and more specifically materials of the LixPOyNz
type with x ~ 2.8 and 2y = 3z with 0.16 ≤ z ≤ 0.46; or
10 LiwPOxNySz with (2x+3y+2z) = (5+w) and 3.2 ≤ x ≤ 3.8; 0.13
≤ y ≤ 0.4; 0 ≤ z ≤ 0.2; 2.9 ≤ w ≤ 3.3; or LitPxAlyOuNvSw
with (5x+3y)=5; (2u+3v+2w) = (5+t); 2.9 ≤ t 3.3; 0.84 ≤ x
≤ 0.94; 0.094 ≤ y ≤ 0.26; 3.2 ≤ u ≤ 3.8; 0.13 ≤ v ≤ 0.46;
0 ≤ w ≤ 0.2; or Li1.9Si0.2P1.0O1.1N1.0; or Li2.9PO3.3N0.46; or
15 Li6-0.75xP1.75xZr2-2xO7-yNz with z ≤ 14/3; 2y = 3z and x ≤ 0.8;
or Li8-3.5xP1.5xZr1-xOz6-yNz with x ≤ 0.8; z ≤ 4 and 2y = 3z;
or Li8-3xLaxZrO6-yNz with O < x ≤ 2; z ≤ 4 and 2y = 3z; or
Li3(Sc2-xMx)(PO4-yNz) with x ≤ 2; z ≤ 8/3; 2y = 3z and M=Al,
Y or Al1-aYa with a<1;
20 c) sulfide-based materials chosen from: LixM1-yM'yS4
with M=Si, Ge, Sn and M'=P, Al, Zn, Ga, Sb; Li2S; B2S3;
P2S5; 70Li2S-30P2S5; Li7P3S11; Li10GeP2S12; Li7PS6;
Li3.25Ge0.25P0.75S4; Li10MP2S12 with M = Si, Ge, Sn and
mixtures between Li2S and one of the compounds among P2S5,
25 GeS2, Ga2S3 or SiS2;
d) phosphate or borate-based materials chosen from
Li3PO4; LiTi(PO4)3; Li1+xAlxM2-x(PO4)3 (where M = Ge, Ti,
and/or Hf and 0 < x 1); Li1.3Al0.3Ti1.7(PO4)3; Li1+x+yAlxTi2-
xSiyP3-yO12 (where 0 ≤ x ≤ 1 and 0 ≤ y ≤ 1); Li1+x+zMx (Ge1-
30 yTiy)2-xSizP3-zO12 (where 0 ≤ x ≤ 0.8, 0 ≤ y ≤ 1.0, 0 ≤ z ≤
0.6); 2(Li1.4Ti2Si0.4P2.6O12)-AlPO4; LixAlz-yGaySw(PO4)c or
LixAlz-yGaySw(BO3)c or LixGez-ySiySw(PO4)c or LixGez-
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WO 2014/131997 7 PCT/FR2014/050424
ySiySw(BO3)c or more generally LixMz-yM'ySw(PO4)c or LixMzyM'ySw(
BO3)c with 4 < w < 20, 3 < x < 10, 0 ≤ y ≤ 1 , 1 ≤
z ≤ 4 and 0 < c < 20 and M or M' an element among Al, Si,
Ge, Ga, P, Zn, Sb; or Li3Sc2-xMxPO4 with M = Al, Y or Al1-
5 aYa with a<1;
e) mixed materials chosen from the mixtures between
Li2S and one of the compounds among Li3PO4, Li3PO4-xN2x/3,
Li4SiO4-xN2x/3, Li4GeO4-xN2x/3 with 0 < x < 4 or Li3ΒO3-xN2x/3
with 0 < x < 3; the mixtures between Li2S and/or B2S3
10 SiS2, P2S5, GeS2, Ga2S3 and a compound of the LiaMOb type,
which may be a lithium silicate Li4SiO4, a lithium borate
Li3BO3 or a lithium phosphate Li3PO4.
According to a specific embodiment, the at least one
Ms bonding material comprises/consists of at least one
15 polymer capable of being impregnated with a lithium salt,
the polymer preferably being chosen from the group formed
by polyethylene oxide, polyimides, vinylidene
polyfluoride, polyacrylonitrile, polymethyl methacrylate,
polysiloxanes, and lithium salt preferably being chosen
20 from the group formed by LiCl, LiBr, LiI, Li(ClO4),
Li(BF4), Li(PF6), Li(AsF6), Li(CH3CO2), Li(CF3SO3),
Li(CF3SO2)2N, Li(CF3SO2)3, Li(CF3CO2), Li(B(C6H5)4),
Li(SCN), Li(NO3).
Advantageously, the thickness of the layer of the at
25 least one Ms bonding material is less than 100 nm,
preferably less than 50 nm, and even more preferably less
than 30 nm.
In a preferred embodiment, the layer containing at
least one Ms bonding material is a nanoparticle layer
30 deposited on at least one of the dense layers obtained in
step a), b) or c). Advantageously, it is deposited by
electrophoresis.
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WO 2014/131997 8 PCT/FR2014/050424
Advantageously, the conductive anode or cathode
current substrates are metal sheets, optionally coated
with a noble metal, or polymer sheets, optionally coated
with a noble metal, or graphite sheets, optionally coated
5 with a noble metal. More specifically, the conductive
anode or cathode current substrates in the form of metal
sheets are aluminum, copper or nickel. More specifically,
the conductive anode or cathode current substrates in the
form of polymer sheets are selected from the following
10 polymers: polyethylene naphthalate (PEN), polyethylene
terephthalate (PET), polypropylene (PP), Teflon® (PTFE),
polyimide (PI) and more specifically Kapton®.
Advantageously, the noble metal is selected from the
following metals: gold, platinum, palladium, vanadium,
15 cobalt, nickel, manganese, niobium, tantalum, chromium,
molybdenum, titanium, palladium, zirconium, tungsten or
any alloy including at least one of these metals.
The invention also relates to an all-solid-state
battery capable of being produced by the process
20 according to the invention, said battery including a
monolithic body formed by at least one dense layer
containing anode materials, at least one dense layer
containing solid electrolyte materials and at least one
dense layer containing cathode materials; preferably, the
25 monolithic body of the battery consists of a plurality of
elementary cells connected in parallel. Advantageously,
the electrical continuity between two adjacent cells is
ensured by the electrolyte.
The battery capable of being obtained by the process
30 according to the invention can be an all-solid-state
multilayer battery.
9
WO 2014/131997 9 PCT/FR2014/050424
In one embodiment of the battery according to the
invention, said battery includes at least one
encapsulation layer, preferably a ceramic or glassceramic
layer. Advantageously, said battery includes a
5 second encapsulation layer deposited on said first
encapsulation layer, said second layer preferably being
made of silicone polymer.
Advantageously, the battery includes terminals where
the cathode and anode current collectors are visible.
10 Preferably, the anode connections and cathode connections
are located on opposite sides of the stack.
Advantageously, the terminals are also covered with a
nickel layer in contact with electrochemical cells, said
nickel layer being covered with a tin layer.
15 Preferably, said at least one encapsulation layer
covers four of the six faces of said battery, the two
other battery faces being covered with terminals.
In certain embodiments, the battery capable of being
obtained by the process according to the invention is
20 entirely inorganic.
Advantageously, the battery obtained according to
the invention is entirely inorganic.
Description of the figures
25 Figures 1(a), 1(b), 1(c), 1(d), 1(e) and 1(f) show
products capable of being obtained according to a
plurality of embodiments according to the invention.
Figure 2 shows a stack of an anode and a cathode
covered with an electrolyte layer and an Ms bonding
30 material layer.
10
WO 2014/131997 10 PCT/FR2014/050424
Figure 3 show a battery capable of being obtained
according to an embodiment of the deposition process of
the invention.
Figures 4 and 5 schematically show the steps for
5 producing a battery according to two embodiments
according to the invention.
Figure 6 schematically shows a cathode film (lefthand
side of the figure) and an anode film covered with
an electrolyte layer (right-hand side of the figure), the
10 two films including patterns cut out by punching. The
black arrow shows the operation of alternate stacking of
cathode and anode sheets covered with electrolyte, with
their cutout patterns stacked in a head-to-tail
configuration. The punching may be performed on the metal
15 substrate before the electrode layers are deposited.
Figure 7 schematically shows a detail of the
stacking of the cathode and anode sheets covered with an
electrolyte layer resulting from the stacking shown in
figure 6.
20 Figure 8 shows a multilayer battery capable of being
obtained by the process according to the invention,
according to a particular embodiment. More specifically,
the multilayer battery includes:
- a plurality of substrate layers 20 made of a metal
25 sheet, or a metal sheet covered with a noble metal, or a
polymer sheet metalized with a noble metal, or a graphite
sheet covered with a noble metal;
- a plurality of solid electrolyte layers 22;
- a plurality of thin anode layers 21;
30 - a plurality of thin cathode layers 24;
- a plurality of Ms bonding material layers (not
shown in the figure);
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WO 2014/131997 11 PCT/FR2014/050424
- at least one thin encapsulation layer 37 capable
of consisting of a polymer, a ceramic or glass-ceramic,
capable of being, for example, in the form of an oxide,
nitride, phosphates, oxynitride or siloxane.
5 Advantageously, this encapsulation layer includes a
ceramic or glass-ceramic layer covered with an epoxy or
silicone resin;
- terminals 35, 36, which make it possible to use
alternately positive and negative electrical connections
10 on each of the ends. These terminals make it possible to
produce electrical connections in parallel between the
different battery elements. For this, only the
connections (+) emerge at one end, and the (-) are
available at the other ends. Preferably, the connections
15 (+) and (-) are laterally offset and the encapsulation
serves as a dielectric substance for preventing the
presence of a short-circuit on said ends. The terminals
35, 36 are shown here as a double layer but may be
produced as a single layer.
20
Detailed description of the invention
Definitions
An "all-solid-state" battery is a battery in which
25 the electrodes and the electrolyte are solid and do not
include a liquid phase, even impregnated in the solid
phase.
An "all-solid-state multilayer battery" according to
the invention is a one-piece battery formed by a stack of
30 a plurality of "elementary cells". An "elementary cell"
in the present invention is an electrochemical cell
consisting of an anode and a cathode with insertion of
12
WO 2014/131997 12 PCT/FR2014/050424
lithium ions, separated by a solid electrolyte conducting
lithium ions.
An "Ms bonding material" refers to any lithium ionconducting
material enabling the anode layer and the
5 cathode layer to be assembled, in which at least one of
said anode and cathode layers is covered with an
electrolyte layer, thermally treated and/or mechanically
compressed, in order to form, by stacking, an all-solidstate
multilayer battery after a low-temperature thermal
10 treatment and/or by mechanical compression of said stack.
In certain embodiments according to the invention
“the batteries are all-inorganic, i.e. they do not
include polymer in the electrodes or in the electrolyte,
but may include elemental carbon (for example graphite).
15 In the context of this invention, a “dense” layer is
a layer having a density greater than 85% of the
theoretical density of the massive body, and preferably
more than 90% or even 95%.
In the context of this invention, the size of a
20 particle is its greatest dimension. Thus, a
“nanoparticle” is a particle in which at least one of the
dimensions is less than 100 nm. The “particle size” or
“average particle size” of a powder or a group of
particles is given as D50.
25
Detailed description
1. Materials for cathode electrolyte and anode
According to the invention, the materials used to
30 produce a cathode layer are preferably, but not entirely,
chosen from one or more of the following materials:
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WO 2014/131997 13 PCT/FR2014/050424
(i) the oxides: LiMn2O4, LiCoO2, LiNiO2,
LiMn1.5Ni0.5O4, LiMn1.5Ni0.5-xXxO4 (where X is selected from
Al, Fe, Cr, Co, Rh, Nd, other rare earth elements, and
where 0 < x < 0.1 ), LiFeO2, LiMn1/3N1/3Co1/3O4;
5 (ii) the phosphates: LiFePO4, LiMnPO4, LiCoPO4,
LiNiPO4, Li3V2(PO4)3; the phosphates of formula LiMNPO4,
with M and N (M N) selected from Fe, Mn, Ni, Co, V;
(iii) all of the lithiated forms of the following
chalcogenides: V2O5, V3O8, TiS2, TiOySz, WOySz, CuS, CuS2.
10 According to the invention, the materials used to
produce an anode layer are preferably, but not entirely,
chosen from one or more of the following materials:
(i) tin oxynitrides (with a typical formula SnOxNy);
(ii) mixed silicon and tin oxynitrides (typical
15 formula SiaSnbOyNz with a>0, b>0, a+b≤2, 00,
b>0, a+b≤2, 0
Documents
Orders
Section
Controller
Decision Date
Application Documents
#
Name
Date
1
5857-DELNP-2015-Response to office action [22-08-2022(online)].pdf
2022-08-22
1
Translations with pct docs.pdf
2015-07-06
2
5857-DELNP-2015-IntimationOfGrant19-08-2022.pdf
2022-08-19
2
specification.pdf
2015-07-06
3
FORM 5.pdf
2015-07-06
3
5857-DELNP-2015-PatentCertificate19-08-2022.pdf
2022-08-19
4
FORM 3.pdf
2015-07-06
4
5857-DELNP-2015-Response to office action [18-08-2022(online)].pdf
2022-08-18
5
drawings.pdf
2015-07-06
5
5857-DELNP-2015-PETITION UNDER RULE 137 [07-06-2022(online)].pdf
2022-06-07
6
5857-DELNP-2015.pdf
2015-07-06
6
5857-DELNP-2015-Written submissions and relevant documents [07-06-2022(online)].pdf
2022-06-07
7
5857-delnp-2015-GPA-(29-07-2015).pdf
2015-07-29
7
5857-DELNP-2015-Correspondence to notify the Controller [24-05-2022(online)].pdf