ELECTROLYTE FOR THIN-FILM ELECTROCHEMICAL DEVICES

专利摘要:
A method of manufacturing an electrolyte for a lithium ion battery or supercapacitor deposited on an electrode, comprising the steps of: a. supplying a conductive substrate, previously covered with a layer of a material that can serve as an electrode ("electrode layer"), b. depositing on said electrode layer an electrolyte layer, preferably by electrophoresis or dip-coating, from a suspension of core-shell particles comprising as a core a particle of a material which can serve as an electrolyte or electrical insulation, on which is grafted a bark comprising PEO; c. Drying of the electrolyte layer thus obtained, preferably under a flow of air; d. optionally, densification of said electrolyte layer by mechanical compression and / or heat treatment.
公开号:FR3080952A1
申请号:FR1853923
申请日:2018-05-07
公开日:2019-11-08
发明作者:Fabien Gaben；Anne-Charlotte Faure
申请人:I TEN；
IPC主号:

专利说明:

SOLID ELECTROLYTE FOR ELECTROCHEMICAL DEVICES
Technical field of the invention
The invention relates to the field of electrochemistry, and more particularly to entirely solid lithium ion batteries. It relates more precisely to solid electrolytes and more particularly to electrolytes in thin layers usable in these electrochemical systems.
The invention also relates to a process for the preparation of such an electrolyte, preferably in a thin layer, which uses nanoparticles of solid electrolyte materials, preferably of lithiated phosphate on which PEO molecules have been grafted, and the electrolytes thus obtained. The invention also relates to a method of manufacturing an electrochemical device comprising at least one of these electrolytes, and the devices thus obtained.
State of the art
A lithium ion battery is an electrochemical component that stores electrical energy. Generally, it is composed of one or more elementary cells, and each cell comprises two electrodes of opposite polarity and an electrolyte. Various types of electrolytes can be used in secondary lithium ion batteries. A cell may include two electrodes separated by a porous polymeric membrane (also called a "separator") impregnated with a liquid electrolyte containing a lithium salt.
By way of example, patent application JP 2002-042792 describes a process for the electrophoretic deposition of a solid electrolyte on an electrode of a battery. The electrolytes described are essentially polymeric membranes such as polyethylene oxide, polyacrylonitrile, poly (vinylidene fluoride) whose pores are impregnated with a lithium salt such as LiPF ₆ . According to the teaching of this document, the size of the particles deposited by electrophoresis must preferably be less than 1 μm, and the layer formed preferably has a thickness less than 10 μm. In such a system, the liquid electrolyte migrates both into the porosities contained in the membrane and towards the electrodes, and thus ensures the ionic conduction between the electrodes.
In order to produce high power batteries and reduce the resistance to transport of lithium ions between the two electrodes, attempts have been made to increase the porosity of the polymer membrane. However, the increased porosity of the polymer matrices facilitates the precipitation of lithium metal dendrites in the pores of the polymer membrane during the charge and discharge cycles of the battery.
These dendrites are the cause of internal short circuits within the cell which can induce a risk of thermal runaway of the battery.
It is known that these polymeric membranes impregnated with a liquid electrolyte have a lower ionic conductivity than the liquid electrolyte used. We can try to compensate for this effect by reducing the thickness of the membranes. However, these polymeric membranes are mechanically fragile and may have their electrical insulation properties altered under the effect of strong electric fields as is the case in batteries charged with very thin films of electrolytes, or under 'effect of mechanical stress and especially vibration. These polymeric membranes tend to break during the charge and discharge cycles, causing detachment of anode and cathode particles; this can cause a short circuit between the two positive and negative electrodes, which can lead to dielectric breakdown. This risk is moreover accentuated in batteries using porous electrodes.
To improve the mechanical strength, Ohara has proposed, in particular in documents EP 1 049 188 A1 and EP 1 424 743 B1, to use electrolytes composed of a polymer membrane containing vitroceramic particles which conduct lithium ions.
Furthermore, it is known from Maunel et al. (Polymer 47 (2006) p.5952-5964) that the addition of ceramic fillers in the polymer matrix makes it possible to improve the morphological and electrochemical properties of polymeric electrolytes; these ceramic fillers may be active (such as Li ₂ N, LiAI ₂ O ₃ ), in which case they participate in the process of transporting lithium ions, or be passive (such as AI ₂ O ₃ , SiO ₂ , MgO), in which case they do not participate in the process of transporting lithium ions. The size of the particles and the characteristics of the ceramic charges influence the electrochemical properties of electrolytes, see Zhang et al., "Flexible and ionconducting membrane electrolytes for solid-state lithium batteries: Dispersions of garnet nanoparticles in insulating POE", NanoEnergy, 28 ( 2016) p.447-454. However, these membranes are relatively fragile and break easily under the effect of mechanical stresses induced during assembly of the batteries.
One of the most studied electrolytic systems is that consisting of poly (ethylene oxide) (, "poly (ethylene oxide" in English, abbreviated here as PEO) in which a lithium salt is dissolved. PEO alone is not a very good conductor of lithium ions, but the integration of liquid electrolytes in the polymer matrix promotes the formation of an amorphous PEO phase, which better conducts lithium ions.
It is known that adding ionic liquids to a PEO matrix impregnated with lithium salts has drawbacks. The first drawback is that it degrades the transport number of the electrolyte: only solid electrolytes without lithium salts or ionic liquids (such as lithiated phosphates) have a transport number equal to 1. The second drawback is that the Chemical stability of high potential PEO is less good when the PEO matrix is impregnated with lithium salts and / or ionic liquids than when it contains nanoparticles of solid electrolyte (see the publication by Zhang cited above). In these electrolytes, conduction is essentially ensured by the nanoparticles; the amorphous phases of the PEO favor the transfer of lithium ions at the interfaces, on the one hand between the particles and on the other hand between the particles and the electrodes.
The deposition of PEO charged with nanoparticles of solid electrolyte, whether the latter is impregnated with a liquid electrolyte or not, is typically done by coating. The addition of nanoparticles of solid electrolyte, however, increases the viscosity of the suspension of the electrolyte used for coating. Too high a viscosity no longer allows a thin layer to be produced by conventional coating techniques. Furthermore, these electrolytes generally remain thick, which contributes to increasing their electrical resistance. And finally, the nanoparticles in these electrolytes are likely to be in the form of agglomerates, which limits their contact surfaces with PEO and therefore affects their efficiency and prevents obtaining good quality thin films. It can be seen that all the electrolytes described in the literature have a particle content of less than 30% by volume.
The present invention aims to remedy at least in part these drawbacks of the prior art.
The problem that the present invention seeks to solve is to provide electrolytes which are safe, usable as a thin layer, which have a high ionic conductivity and a transport number close to 1, a stable mechanical structure and a long service life.
Another problem which the present invention seeks to solve is to provide a method for manufacturing such an electrolyte which is simple, safe, rapid, easy to implement, easy to industrialize and inexpensive.
Another object of the invention is to provide electrolytes for batteries capable of operating reliably and without the risk of fire.
Another objective of the invention is to provide a battery with a rigid structure having a high power density capable of mechanically withstanding shocks and vibrations.
Another objective of the invention is to provide a method of manufacturing an electronic, electrical or electrotechnical device such as a battery, a capacitor, a supercapacitor, a photovoltaic cell comprising an electrolyte according to the invention.
Another objective of the invention is to provide devices such as batteries, lithium ion battery cells, capacitors, supercapacitors, photovoltaic cells having increased reliability, having a long lifetime and which can be encapsulated. by coatings deposited by the atomic layer deposition technique (ALD, Atomic Layer Deposition), at high temperature and under reduced pressure.
Objects of the invention
According to the invention the problem is resolved by the use of at least one electrolyte which has a homogeneous composite structure comprising a volume ratio of solid electrolyte / PEO greater than 35%, preferably greater than 50%, preferably greater than 60%, and even more preferably greater than 70% by volume. The high content of solid electrolyte combined with its homogeneous dispersion gives this structure good mechanical strength. A second object of the invention is a method of manufacturing an electrolyte, preferably in a thin layer, for a lithium ion battery or supercapacitor, deposited on an electrode, comprising the steps of:
at. supply of a conductive substrate, previously covered with a layer of a material which can serve as an electrode ("electrode layer"),
b. deposition on said electrode layer of an electrolyte layer, preferably by electrophoresis or by dip-coating, from a suspension of core-shell particles comprising as core, a particle of a material which can serve as electrolyte or of electronic insulator, on which is grafted a bark comprising PEO;
vs. Drying of the electrolyte layer thus obtained, preferably under an air flow;
d. optionally, densification of said electrolyte layer by mechanical compression and / or heat treatment.
Preferably, the average size D ₅₀ of the core primary particles is less than 100 nm, preferably less than 50 nm and even more preferably less than or equal to 30 nm. Advantageously, the primary core particles are obtained by hydrothermal or solvothermal synthesis.
Advantageously, the thickness of the shell of the core-shell particles is between 1 nm and 100 nm.
Advantageously, the electrolyte layer obtained in step c) or d) has a thickness of less than 5 μm, preferably around 3 μm.
Advantageously, the PEO has a weight-average molecular mass of less than 7000 g / mol, preferably around 5000 g / mol.
Advantageously, the dry extract of the suspension of core-shell particles used in step b) is less than 30% by mass.
The process according to the invention can be used for the manufacture of electrolytes, preferably in a thin layer, in electronic, electrical or electrotechnical devices, and preferably in devices selected from the group formed by: batteries, capacitors, supercapacitors, capacitors, resistors, inductors, transistors.
Another object of the invention is an electrolyte capable of being obtained by the method according to the invention, preferably a thin film electrolyte.
Advantageously, the electrolyte according to the invention, preferably in a thin layer, comprising a solid electrolyte and PEO, has a solid electrolyte / PEO volume ratio greater than 35%, preferably greater than 50%, preferably greater than 60%. , and even more preferably greater than 70%.
Advantageously, the electrolyte according to the invention, preferably in a thin layer, has a porosity of less than 20%, preferably less than 15%, even more preferably less than 10%.
Another object of the invention is an electrochemical device comprising at least one electrolyte, preferably a thin film electrolyte, according to the invention, preferably a lithium ion battery or a supercapacitor.
Another object of the invention is a method for manufacturing a lithium ion battery implementing the method according to the invention, and comprising the steps of:
i. Supply of at least two conductive substrates which can serve as battery current collectors, previously covered with a layer of a material which can serve as an anode and respectively as a cathode (“anode layer” respectively “cathode layer”) , and being covered on at least part of at least one of their faces with a layer of cathode, respectively of anode, ii. Supply of a colloidal suspension comprising core-shell nanoparticles comprising as core a particle of a material which can be used as an electrolyte or electronic insulator, onto which a shell comprising PEO is grafted, iii. Deposition of an electrolyte layer, preferably by electrophoresis or by dip-coating, from a suspension of core-shell particles obtained in step ii), on the cathode, and / or anode layer obtained in step i), to obtain a first and / or a second intermediate structure, iv. Drying of the layer thus obtained in step iii), preferably under an air flow,
v. Realization of a stack from said first and / or second intermediate structure to obtain a stack of the “substrate / anode / electrolyte / cathode / substrate” type:
• either by depositing an anode layer on said first intermediate structure, • or by depositing a cathode layer on said second intermediate structure, • or by superimposing said first intermediate structure and said second intermediate structure so that the two layers electrolyte are placed one on top of the other, vi. Densification of the stack obtained in the previous step by mechanical compression and / or heat treatment of the stack leading to the production of a cell, preferably a battery.
When the battery obtained in step vi) comprises at least one cathode layer and / or at least one porous, preferably mesoporous anode layer, the process for manufacturing a lithium ion battery according to the invention, comprises a step of impregnating the battery obtained in step vi) with a phase carrying lithium ions leading to the production of an impregnated battery.
Advantageously, said material which can serve as electronic insulator is preferably chosen from AI ₂ O ₃ , SiO ₂ , ZrO ₂ .
Advantageously, the cathode is a dense electrode or a dense electrode coated with ALD with an electronically insulating layer, preferably with an electronically insulating and ionically conductive layer, or a porous electrode or a porous electrode coated with ALD with an insulating layer electronically, preferably an electronically insulating and ionically conductive layer or, preferably, a mesoporous electrode, or a mesoporous electrode coated by ALD with an electronically insulating layer, preferably an electronically insulating and ionically conductive layer and / or wherein the anode is a dense electrode or a dense electrode coated with ALD with an electronically insulating layer, preferably with an electronically insulating and ionically conductive layer, or a porous electrode or a porous electrode coated with ALD with a layer electronically insulating, preferably an insulating layer electronically and ionically conductive ante or, preferably, a mesoporous electrode or a mesoporous electrode coated by ALD with an electronically insulating layer, preferably with an electronically insulating and ionically conductive layer.
Advantageously, after step vi) or after the impregnation step:
successively, alternately, on the battery:
o at least a first layer of parylene and / or polyimide on said battery, o at least a second layer composed of an electrically insulating material by ALD (Atomic Layer Deposition) on said first layer of parylene and / or polyimide, o and on the alternating succession of at least a first and at least a second layer is deposited a layer making it possible to protect the battery against mechanical damage to the battery, preferably made of silicone, epoxy resin or parylene, or in polyimide thus forming a battery encapsulation system, the battery thus encapsulated is cut along two section planes to expose anode and cathode connections of the battery on each of the sectional planes, so that the system encapsulation coating four of the six faces of said battery, preferably continuously, successively depositing, on and around, these anodic and cathodic connections ques:
o an optional first electronically conductive layer, preferably deposited by ALD, o a second layer based on silver-charged epoxy resin, deposited on the first electronically conductive layer, and o a third layer based on nickel, deposited on the second layer, and o a fourth layer based on tin or copper, deposited on the third layer.
Preferably, the anode and cathode connections are on the opposite sides of the stack.
Description of the invention
For the purpose of this document, the size of a particle is defined by its largest dimension. By “nanoparticle” is meant any particle or object of nanometric size D ₅₀ having at least one of its dimensions less than or equal to 100 nm.
In the context of this document, an electronically insulating material or layer, preferably an electronically insulating and ionically conductive layer, is a material or layer whose electrical resistivity (resistance to passage of electrons) is greater than 10 ⁵ Ω-cm.
By “mesoporous” materials is meant any solid which has within its structure pores called “mesopores” having a size intermediate between that of the micropores (width less than 2 nm) and that of the macropores (width greater than 50 nm), namely a size between 2 nm and 50 nm. This terminology corresponds to that adopted by IUPAC (International Union for Pure and Applied Chemistry), which is used by those skilled in the art. The term “nanopore” is therefore not used here, even if the mesopores as defined above have nanometric dimensions within the meaning of the definition of nanoparticles, knowing that the pores of size smaller than that of the mesopores are called by the skilled in the art of "micropores".
A presentation of the concepts of porosity (and of the terminology which has just been exposed above) is given in the article "Texture of pulverulent or porous materials" by F. Rouquerol et al. published in the "Engineering techniques" collection, Treatise on Analysis and Characterization, booklet P 1050; this article also describes the porosity characterization techniques, in particular the BET method.
For the purposes of the present invention, the term “mesoporous layer” means a layer which has mesopores.
To implement the method according to the invention, nanoparticles of electrolyte or electronic insulator are supplied, preferably in the form of a suspension in a liquid phase. The electrolyte nanoparticles can be produced by nanogrinding / dispersion of a solid electrolyte powder (or electronic insulator) or by hydrothermal synthesis or by solvothermal synthesis or by precipitation. Preferably, a method will be chosen which makes it possible to obtain primary nanoparticles of very homogeneous size (monodisperse). The solvothermal, for example hydrothermal, route is preferred, which leads to nanoparticles having a very homogeneous size, good crystallinity and purity, while nanogrinding tends to deteriorate solid nanoparticles. The synthesis of nanoparticles by precipitation also makes it possible to obtain primary nanoparticles of very homogeneous size, of good crystallinity and purity.
1. Functionalization of nanoparticles of material that can serve as electrolyte or electronic insulator by PEO
The electrolyte or electronic insulator nanoparticles can then be functionalized with organic molecules in a liquid phase, according to methods known to those skilled in the art. Functionalization consists in grafting onto the surface of the nanoparticles a molecule having a structure of the Q-Z type in which Q is a function ensuring the attachment of the molecule to the surface, and Z is a PEO group.
As group Q, a complexing function of the surface cations of the nanoparticles can be used such as the phosphate or phosphonate function.
Preferably, the electrolyte or electronic insulator nanoparticles are functionalized with a PEO derivative of the type
where X represents an alkyl chain or a hydrogen atom, n is between 40 and 10,000 (preferably between 50 and 200), m is between 0 and 10, and
Q ’is an embodiment of Q and represents a group selected from the group formed by:
O — P — OR / I
GOLD
GOLD
I --P —O
I □ R
---- If (DR ') ₃

and where R represents an alkyl chain or a hydrogen atom, R ’represents a methyl group or an ethyl group, x is between 1 and 5, and x’ is between 1 and 5.
More preferably, the nanoparticles of electrolyte or electronic insulator are functionalized with methoxy-PEO-phosphonate
where n is between 40 and 10,000 and preferably between 50 and 200.
According to an advantageous embodiment, a solution of QZ (or Q'-Z, where appropriate) is added to a colloidal suspension of nanoparticles of electrolyte or electronic insulator so as to obtain a molar ratio between Q (which comprises here Q ') and all of the cations present in the nanoparticles of electrolyte or electronic insulator (abbreviated here "NP-E") between 1 and 0.01, preferably between 0.1 and 0.02. Beyond an A / NP-E molar ratio of 1, the functionalization of the electrolyte nanoparticles or of electronic insulator by the QZ molecule risks inducing steric hindrance such that the electrolyte particles cannot be fully functional; it also depends on the particle size. For a Q / NP-E molar ratio of less than 0.01, the Q-Z molecule may not be in sufficient quantity to ensure sufficient conductivity of the lithium ions; it also depends on the particle size. Using more Q-Z during functionalization would consume unnecessary Q-Z.
Advantageously, the material which can serve as electronic insulator is preferably chosen from AI ₂ O ₃ , SiO ₂ , ZrO ₂ , and / or a material selected from the group formed by the electrolyte materials below.
Advantageously, the electrolyte nanoparticles are chosen from:
o garnets of formula Li _d A ¹ x A ² y (TO ₄ ) _z where
A ¹ represents a cation of oxidation state + II, preferably Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; and or
A ² represents a cation of oxidation state + III, preferably Al, Fe, Cr, Ga, Ti, La; and where (TO ₄ ) represents an anion in which T is an atom of degree of oxidation + IV, located at the center of a tetrahedron formed by the oxygen atoms, and in which TO ₄ advantageously represents the silicate anion or zirconate, knowing that all or part of the elements T of an oxidation state + IV can be replaced by atoms of an oxidation state + III or + V, such as Al, Fe, As, V, Nb, In, Ta;
knowing that: d is between 2 and 10, preferably between 3 and 9, and even more preferably between 4 and 8; x is between 2.6 and 3.4 (preferably between 2.8 and 3.2); y is between 1.7 and 2.3 (preferably between 1.9 and 2.1) and z is between 2.9 and 3.1;
o garnets, preferably chosen from: oxides of the LLZO type, Li ₇ La ₃ Zr ₂ 0i ₂ ; Li6La ₂ BaTa ₂ 0i2; Li5,5La ₃ Nb _1i7 5lno. ₂ 50i ₂ ; Li5La ₃ M ₂ 0i ₂ with M = Nb or Ta or a mixture of the two compounds; the Li ₇ . _x Ba _x La ₃ . _x M ₂ 0i ₂ with 0 <x <1 and M = Nb or Ta or a mixture of the two compounds; the Li ₇ . _x La ₃ Zr ₂ . _x M _x Oi ₂ with 0 <x <2 and M = Al, Ga or Ta or a mixture of two or three of these compounds;
o lithiated phosphates, preferably chosen from: lithiated phosphates of the NaSICON type, Li ₃ PO ₄ ; LiPO ₃ ; Li ₃ Alo, ₄ Sc _1i6 (P0 ₄ ) ₃ called “LASP”; Li ₃ (Sc _{2. x} M _x ) (PO ₄ ) ₃ with M = AI or Y and 0 <x <1; Li _{1 + x} M _x (Sc) ₂ . _x (PO ₄ ) ₃ with M = Al, Y, Ga or a mixture of the three compounds and 0 <x <0.8; Li _{1 + x} M _x (Ga _{1. y} Sc _y ) ₂ . _x (PO ₄ ) ₃ with 0 <x <0.8; 0 <y <1 and M = Al or Y or a mixture of the two compounds; Li _{1 + x} M _x (Ga) ₂ . _x (PO ₄ ) ₃ with M = Al, Y or a mixture of the two compounds and 0 <x <0.8; Li _{1 + x} Al _x Ti ₂ . _x (PO ₄ ) ₃ with 0 <x <1 called "LATP"; or Li _{1 + x} Al _x Ge ₂ . _X (PO ₄ ) ₃ with 0 <x <1 called "LAGP"; or Lh + x + zM ^ GevyTiyl ^ xSizPs-zO ^ with 0 <x <0.8 and 0 <y <1.0 and 0 <z <0.6 and M = Al, Ga or Y or a mixture of two or three of these compounds; Li _{3 + y} (Sc _{2. x} M _x ) QyP ₃ .yOi ₂ with M = Al and / or Y and Q = Si and / or Se, 0 <x <0.8 and 0 <y <1; or Li _{1 + x + y} M _x Sc ₂ . _x QyP ₃ . _y Oi ₂ 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 Lh + x + y + zM ^ GavySCyl ^ xQzPs-zO ^ 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; or Li _{1 + X} M ³ _X M ₂ . _x P ₃ 0i ₂ with 0 <x <1 and M ³ = Cr and / or V, M = Sc, Sn, Zr, Hf, Se or Si, or a mixture of these compounds;
o the lithiated borates, preferably chosen from: Li ₃ (Sc _{2. x} M _x ) (BO ₃ ) ₃ with M = AI or Y and 0 <x <1; Li _{1 + x} M _x (Sc) ₂ . _x (BO ₃ ) ₃ with M = Al, Y, Ga or a mixture of the three compounds and 0 <x <0.8; Lh + xM ^ GavySCy ^ BOsIs with 0 <x <0.8.0 <y <1 and M = Al or Y; Li _{1 + x} M _x (Ga) ₂ . _x (BO ₃ ) ₃ with M = Al, Y or a mixture of the two compounds and 0 <x <0.8; Li ₃ BO ₃ , Li ₃ BO ₃ -Li ₂ SO ₄ , Li ₃ BO ₃ -Li ₂ SiO ₄ , Li ₃ BO ₃ Li ₂ SiO ₄ -Li ₂ SO ₄ ;
o oxynitrides, preferably chosen from Li ₃ PO ₄ . _x N _{2x / 3} , Li ₄ SiO ₄ . _x N _{2x / 3} , Li ₄ GeO ₄ . _x N _{2x / 3} with 0 <x <4 or Li ₃ BO ₃ . _x N _{2x / 3} with 0 <x <3;
o the lithiated compounds based on lithium oxynitride and phosphorus, called “LiPON”, in the form of Li _x PO _y N _z with x ~ 2.8 and 2y + 3z ~ 7.8 and 0.16 <z < 0.4, and in particular Li ₂ , ₉ P0 ₃ , ₃ No, ₄ 6, but also the compounds Li _w PO _x N _y S _z with 2x + 3y + 2z = 5 = w or the compounds Li _w PO _x N _y S _z with 3.2 <x <3.8, 0.13 <y <0.4, 0 <z <0.2, 2.9 <w <3.3 or the compounds in the form of LitP _x al _y O _w with _u NvS 5x + 3y = 5, 2u + 3v + 2w + t = 5, 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;
o materials based on lithium oxynitrides of phosphorus or boron, called respectively "LiPON" and "LIBON", which can also contain silicon, sulfur, zirconium, aluminum, or a combination of aluminum, boron, sulfur and / or silicon, and boron for materials based on phosphorus lithium oxynitrides;
o the lithiated compounds based on lithium oxynitride, phosphorus and silicon called "LiSiPON", and in particular Lir9Sio.28P1.oO1.1Nro;
o lithium oxynitrides of LiBON, LiBSO, LiSiPON, LiSON, thioLiSiCON, LiPONB types (or B, P and S represent boron, phosphorus and sulfur respectively);
o LiBSO type lithium oxynitrides such as (1-x) LiBO ₂ - xLi ₂ SO ₄ with 0.4 <x <0.8;
o the lithiated oxides, preferably chosen from Li ₇ La ₃ Zr ₂ 0i ₂ or LÎ5 _{+ x} La ₃ (Zr _x , A _{2. x} ) Oi2 with A = Sc, Y, Al, Ga and 1,4 < x <2 or Li _{0, 3 0} 5The, 55TiO ₃ or Li _3x La _{2/3. x} TiO ₃ with 0 <x <0.16 (LLTO);
o silicates, preferably chosen from Li ₂ Si ₂ O5, Li ₂ SiO ₃ , Li ₂ Si ₂ O ₆ , LiAISiO ₄ , Li ₄ SiO ₄ , LiAISi ₂ O ₆ ;
o solid electrolytes of anti-perovskite type chosen from: Li ₃ OA with A halide or a mixture of halides, preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these; Li _{(3. X} ) Mx / ₂ OA with 0 <x <3, M a divalent metal, preferably at least one of the elements chosen from Mg, Ca, Ba, Sr or a mixture of two or three or four of these elements , A halide or a mixture of halides, preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these elements; Li _{(3. X} ) M ³ x / 3OA with 0 <x <3, M ³ a trivalent metal, A a halide or a mixture of halides, preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these; or LiCOXzY ₍ i. _Z ), with X and Y halides as mentioned above in relation to A, and 0 <z <1, o the compounds La ₀ , ₅ iLi ₀ , ₃₄ Ti ₂ , ₉₄ , Li ₃ , ₄ V ₀ , ₄ Ge ₀ , 6O ₄ , Li ₂ O-Nb ₂ O ₅ ;
o formulations based on Li ₂ CO ₃ , B ₂ O ₃ , Li ₂ O, AI (PO ₃ ) ₃ LiF,, Li ₃ N, Lii ₄ Zn (GeO ₄ ) ₄ , Li _3i6 Ge ₀ , 6Vo, ₄ 0 ₄ , LiTi ₂ (PO ₄ ) ₃ , Lii _i3 Alo, ₃ Tii ₇ (PO ₄ ) ₃ , Lii + xAl _x M ₂ .x (PO ₄ ) ₃ (where M = Ge, Ti, and / or Hf, and where 0 <x <1), Lii _{+ x +} yAlxTi ₂ .xSiyP ₃ . _y Oi ₂ (where 0 <x <1 and 0 <y <1).
A colloidal suspension of electrolyte nanoparticles at a mass concentration of between 0.1% and 50%, preferably between 5% and 25%, and even more preferably at 10%, is used to effect the functionalization of the electrolyte particles. At high concentrations, there may be a risk of bridging and a lack of accessibility of the surface to be functionalized (risk of precipitation of non or poorly functionalized particles). Preferably, the electrolyte nanoparticles are dispersed in a liquid phase such as water or ethanol.
This reaction can be carried out in any suitable solvent allowing the Q-Z molecule to be dissolved.
Depending on the Q-Z molecule, the functionalization conditions can be optimized, in particular by adjusting the temperature and the duration of the reaction, and the solvent used. After having added a solution of QZ to a colloidal suspension of electrolyte nanoparticles, the reaction medium is left under stirring for 0 h to 24 hours (preferably for 5 minutes to 12 hours, more preferably still for 0.5 hours to 2 hours), so that at least some, preferably all of the QZ molecules can be grafted onto the surface of the electrolyte nanoparticles. The functionalization can be carried out under heating, preferably at a temperature between 20 ° C and 100 ° C. The temperature of the reaction medium must be adapted to the choice of the functionalizing molecule Q-Z.
These functionalized nanoparticles therefore have a core (“heart”) made of electrolyte material and a shell made of PEO. The thickness of the bark can typically be between 1 nm and 100 nm; this thickness can be determined by transmission electron microscopy, typically after labeling the polymer with ruthenium oxide (RuO ₄ ).
Advantageously, the nanoparticles thus functionalized are then purified by cycles of successive centrifugations and redispersions and / or by tangential filtration. In one embodiment, the colloidal suspension of functionalized electrolyte nanoparticles is centrifuged so as to separate the functionalized particles from the unreacted Q-Z molecules present in the supernatant. After centrifugation, the supernatant is removed. The pellet comprising the functionalized particles is redispersed in the solvent. Advantageously, the pellet comprising the functionalized particles is redispersed in an amount of solvent making it possible to reach the desired dry extract. This redispersion can be carried out by any means, in particular by the use of an ultrasonic bath or again with magnetic and / or manual stirring.
Several cycles of successive centrifugations and redispersions can be carried out so as to eliminate the unreacted Q-Z molecules. Preferably at least one, and even more preferably at least two successive cycles of centrifugation and redispersions is carried out.
After redispersion of the functionalized electrolyte nanoparticles, the suspension can be reconcentrated until the desired dry extract is reached, wherever appropriate.
Advantageously, the dry extract of a suspension of electrolyte nanoparticles functionalized with PEO comprises more than 40% (by volume) of solid electrolyte material, preferably more than 60% and even more preferably more than 70% of material. solid electrolyte.
2. Development of an electrolyte layer from electrolyte nanoparticles or electronic insulator functionalized with PEO according to the invention
According to the invention, the solid electrolyte can be deposited electrophoretically, by the coating process, by soaking (called "dip-coating" in English), or by other deposition techniques known to those skilled in the art. profession allowing the use of a suspension of electrolyte nanoparticles or electronic insulator functionalized by PEO.
Advantageously, the dry extract of the suspension of electrolyte nanoparticles or electronic insulator functionalized with PEO used to deposit an electrolyte layer electrophoretically, by dip-coating or by other known deposition techniques of the skilled person according to the invention is less than 30% by mass; such a suspension is sufficiently stable during deposition. Preferably, the solid electrolyte is deposited electrophoretically or by dip-coating. These two techniques advantageously make it possible to easily produce compact layers without defects.
- Electrophoretic deposition of electrolyte nanoparticles or electronic insulator functionalized with PEO
The process according to the invention can use the electrophoresis of nanoparticle suspensions as a technique for depositing porous layers. The process for depositing layers from a suspension of nanoparticles is known as such (see for example EP 2 774 208 B1). The electrophoretic deposition of particles functionalized with PEO is done by the application of an electric field between the substrate on which the deposition is carried out, and a counter-electrode, making it possible to set the charged particles of the colloidal suspension in motion, and to deposit them on the substrate. To ensure the stability of the colloidal suspension, polar nanoparticles are preferably used, and / or the colloidal suspension advantageously has a Zeta potential in absolute value greater than 25 mV.
The electrophoretic deposition rate is a function of the applied electric field and the electrophoretic mobility of the particles in the suspension. It can be very high. For example, for an applied voltage of 200 V, the deposition rate can reach around 10 pm / min.
The inventor has found that this technique makes it possible to deposit very homogeneous layers over very large surfaces (provided that the concentration of particles and the electric field are homogeneous on the surface of the substrate). Electrophoresis deposition can be implemented in a “batch” (static) type process or in a continuous process.
The electrolyte layer is deposited on an anode layer and / or a cathode layer themselves formed on a conductive substrate by an appropriate method, and / or directly on a sufficiently conductive substrate.
As an example, a metallic substrate, such as a stainless steel strip, which may be, for example, a thickness of 5 μm, may be used as a conductive substrate, or a polymer strip having an electrically conductive surface layer. The deposition of the anode and cathode layers can be carried out on this type of conductive substrate by any suitable means. These anode and cathode layers can be dense, i.e. have a volume porosity of less than 20%. They can also be porous, and in this case it is preferred that they have an interconnected network of open porosity; this porosity is preferably a mesoporosity, with pores with an average diameter of between 2 nm and 50 nm. During electrophoretic deposition, a stabilized supply makes it possible to apply a voltage between the conductive substrate and two electrodes located on either side of this substrate. This voltage can be continuous or alternating. Precise monitoring of the currents obtained makes it possible to precisely monitor and control the thicknesses deposited.
The deposition of an electrolyte layer by electrophoresis allows perfect coverage of the surface of the electrode layer regardless of its geometry, even in the presence of roughness defects. It therefore makes it possible to guarantee the dielectric properties of the layer.
Electrophoresis deposition avoids the use of organic binders, since compact layers are obtained directly. The compactness of the layer obtained by electrophoretic deposition, and the absence of a large amount of organic compounds in the layer makes it possible to limit or even avoid the risks of cracks or the appearance of other defects in the layer during the stages of drying. A mechanical compaction step can be carried out, for example by pressing, before drying in order to improve the quality of the layer; this does not replace mechanical densification after drying, the effect of which is different.
- Deposition of electrolyte nanoparticles or electronic insulator functionalized by PEO
Nanoparticles of electrolyte or electronic insulator functionalized with PEO can be deposited in particular by the coating process, by soaking (called “dip-coating” in English), or by other deposition techniques known from the skilled in the art, regardless of the chemical nature of the nanoparticles used. This deposition process is preferred when the nanoparticles of electrolyte or electronic insulator functionalized with PEO have little or no electronic charge. In order to obtain a layer of a desired thickness, the step of deposition by dip-coating of the electrolyte or electronic insulator nanoparticles functionalized with PEO followed by the step of drying the layer obtained are repeated as much as necessary.
Although this succession of steps of coating by dipping / drying is time-consuming, the deposition process by dip-coating is a simple, safe process, easy to implement and to industrialize, and it makes it possible to obtain a final layer. homogeneous and compact.
- Drying and densification of the layer of electrolyte nanoparticles or electronic insulator functionalized with PEO
After deposition, whether by electrophoresis or by dip-coating, the layer of nanoparticles obtained must be dried. Drying must not induce the formation of cracks. For this reason it is preferred to perform it under controlled humidity and temperature conditions.
Advantageously, these layers have crystalline electrolyte or electronic insulator nanoparticles bonded together by amorphous PEO. Advantageously, these layers have a content of nanoparticles of electrolyte or electronic insulator greater than 35%, preferably greater than 50%, preferably greater than 60% and even more preferably greater than 70% by volume.
The use of nanoparticles of electronic insulator limits the self-discharge of the battery and contributes to the amorphization of the PEO.
Advantageously, the electrolyte or electronic insulator nanoparticles present in these layers have a size D _{50 of} less than 100 nm, preferably less than 50 nm and even more preferably less than or equal to 30 nm; this value refers to the "heart" of the "heart - bark" nanoparticles. This particle size ensures good conductivity of lithium ions between the electrolyte particles and the PEO.
The electrolyte layer obtained after drying has a thickness of less than 10 μm, preferably less than 5 μm, preferably of approximately 3 μm in order to limit the thickness and the weight of the battery without reducing its properties.
After drying, the layer of nanoparticles can be densified; this step is optional.
Densification makes it possible to reduce the porosity of the layer. The structure of the layer obtained after densification is continuous, almost without porosities, and the ions can migrate there easily, without the need to add liquid electrolytes containing lithium salts, such liquid electrolytes being at the origin poor thermal resistance of batteries containing thermal performance, and poor aging resistance. The layers based on solid electrolyte and PEO obtained after drying and densification generally have a porosity of less than 20%, preferably less than 15% by volume, even more preferably less than 10% by volume, and optimally less than 5% by volume. This value can be determined by transmission electron microscopy.
The densification of the layer after its deposition can be carried out by any suitable means, preferably:
a) by any mechanical means, in particular by mechanical compression, preferably uniaxial compression;
b) by thermocompression, i.e. by pressure heat treatment. The optimal temperature strongly depends on the chemical composition of the powders deposited, it also depends on the particle sizes and the compactness of the layer. A controlled atmosphere is preferably maintained in order to avoid oxidation and surface pollution of the particles deposited. Advantageously, the compaction is carried out under a controlled atmosphere and at temperatures between room temperature and the melting temperature of the PEO used; thermocompression can be carried out at a temperature between room temperature (about 20 ° C) and about 300 ° C; but we prefer not to exceed 200 ° C (or even more preferably 100 ° C) in order to avoid degradation of the PEO.
The densification of the electrolyte or electronic insulator nanoparticles functionalized with PEO can be obtained only by mechanical compression (application of mechanical pressure) because the shell of these nanoparticles comprises PEO, a polymer easily deformable at relatively low pressure. . Advantageously, the compression is carried out in a pressure range between 10 MPa and 500 MPa, preferably between 50 MPa and 200 MPa and at a temperature of the order of 20 ° C to 200 ° C.
At the interfaces, the PEO is amorphous and ensures good ionic contact between the particles of solid electrolytes. PEO can thus conduct lithium ions, even in the absence of liquid electrolyte. It promotes the assembly of the lithium ion battery at low temperature, thus limiting the risk of interdiffusion at the interfaces between the electrolytes and the electrodes.
The electrolyte layer obtained after densification has a thickness of less than 10 μm, preferably less than 5 μm, preferably of approximately 3 μm in order to limit the thickness and the weight of the battery without reducing its properties.
The densification process which has just been described can be carried out during assembly of the battery, which will be described below.
3. Assembly of a battery comprising an electrolyte layer obtained from electrolyte nanoparticles or electronic insulator functionalized with PEO according to the invention
One of the aims of the invention is to provide new electrolytes, preferably in a thin layer, for secondary batteries with lithium ions. We describe here the production of a battery with an electrolyte according to the invention.
A suspension of nanoparticles of precursor material of an electrolyte layer according to the invention can be prepared by precipitation or by solvothermal, in particular hydrothermal, route, which leads directly to nanoparticles of good crystallinity. The electrolyte layer is deposited by electrophoresis or by dip coating on a cathode layer covering a substrate and / or on an anode layer covering a substrate; in both cases said substrate must have sufficient conductivity to be able to act as a cathode or anode current collector, respectively. The assembly of the cell formed by an anode layer, the electrolyte layer according to the invention and a cathode layer is carried out by hot pressure, preferably under an inert atmosphere. The temperature is advantageously between 20 ° C and 300 ° C, preferably between 20 ° C and 200 ° C, and even more preferably between 20 ° C and 100 ° C. The pressure is advantageously uniaxial and between 10 MPa and 200 MPa, and preferably between 50 MPa and 200 MPa.
A cell is thus obtained which is completely solid and rigid.
We describe here another example of manufacturing a lithium ion battery according to the invention. This process includes the steps of:
(1) Supply of at least two conductive substrates previously covered with a layer of a material which can serve as an anode and, respectively, as a cathode (these layers being called “anode layer” and “cathode layer”), (2) Supply of a colloidal suspension of core-shell nanoparticles comprising particles of a material which can serve as electrolyte, onto which a PEO shell is grafted, (3) Deposition of a layer of said core-shell nanoparticles by electrophoresis or by dip-coating, from said colloidal suspension on at least one cathode or anode layer obtained in step (1), (4) Drying of the electrolyte layer thus obtained, preferably under a air flow, (5) Stacking of the cathode and anode layers, (6) Treatment of the stacking of the anode and cathode layers obtained in step (5) by mechanical compression and / or the rmique so as to assemble the electrolyte layers present on the anode and cathode layers.
Advantageously, the anode and cathode layers can be dense electrodes, ie electrodes having a volume porosity of less than 20%, porous electrodes, preferably having an interconnected network of open pores or mesoporous electrodes, preferably having a interconnected network of open mesopores.
Due to the very large specific surface area of porous, preferably mesoporous, electrodes, when used with a liquid electrolyte, parasitic reactions can occur between the electrodes and the electrolyte; these reactions are at least partially irreversible. In an advantageous embodiment, a very thin layer of an electronically insulating material, which is preferably ionic conductor, is applied to the layer of porous electrode, preferably mesoporous, in order to block these parasitic reactions.
In the context of dense electrodes and in another advantageous embodiment, a very thin layer of an electronically insulating material, which is preferably ionic conductor, is applied to the electrode layer in order to reduce the interfacial resistance existing between the dense electrode and electrolyte.
This layer of electronically insulating material, which is preferably an ionic conductor, advantageously has an electronic conductivity of less than 10 ⁸ S / cm. Advantageously, this deposition is carried out at least on one face of the electrode, whether it is porous or dense, which forms the interface between the electrode and the electrolyte. This layer can for example be made of alumina, silica, or zirconia. On the cathode you can use
Ι_ί ₄ Τί ₅ Οΐ2θυ another material which, like Li ₄ Ti ₅ 0i2, has the characteristic of not inserting, at the operating voltages of the cathode, lithium and behaving like an electronic insulator.
Alternatively, this layer of an electronically insulating material can be an ionic conductor, which advantageously has an electronic conductivity of less than 10 ' ⁸ S / cm. This material must be chosen so as not to insert lithium at the operating voltages of the battery, but only to transport it. As such, Li ₃ PO ₄ , Li ₃ BO ₃ , lithium lanthanum zirconium oxide (called “LLZO”), such as Li ₇ La ₃ Zr ₂ 0 ₂ , which have a wide range of potential, can be used in this respect. Operating. In contrast, the titanium oxide lanthanum lithium (abbreviated "LLTO"), such as Li _3x La ₂ / _3x TiO _3, lithium aluminum titanium phosphate (abbreviated as "PAL"), lithium aluminum germanium phosphate (abbreviated "LAGP »), Can only be used in contact with the cathodes because their operating potential range is restricted; beyond this range they are likely to insert lithium into their crystallographic structure.
This deposition further improves the performance of lithium ion batteries having at least one electrode, whether porous or dense. In the case of porous impregnated electrodes, this deposit makes it possible to reduce the faradaic interface reactions with the electrolytes. These parasitic reactions are all the more important the higher the temperature; they are the cause of reversible and / or irreversible loss of capacity. In the case of dense electrodes in contact with the solid electrolyte it also makes it possible to limit the interface resistances linked to the appearance of space charges.
Very advantageously, this deposition is carried out by a technique allowing an enveloping coating (also called "conformal deposition"), i.e. a deposition which faithfully reproduces the atomic topography of the substrate to which it is applied. The technique of ALD (Atomic Layer Deposition), known as such, may be suitable. It can be used on dense electrodes before the deposition of the electrolyte layer and before assembly of the cell. It can be implemented on porous, preferably mesoporous electrodes before and / or after the deposition of the electrolyte layer and before assembly of the cell. The deposition technique by ALD is done layer by layer, by a cyclic process, and makes it possible to produce a coating coating which faithfully reproduces the topography of the substrate; it lines the entire surface of the electrodes. This coating coating typically has a thickness of between 1 nm and 5 nm.
When the electrodes used are porous and covered with a nanolayer of an electronically insulating material, preferably ionic conductor, it is preferable that the primary diameter D ₅₀ of the particles of electrode material used to produce them is at least 10 nm in order to prevent the layer of electronically insulating material, preferably ionic conductor, from blocking the open porosity of the electrode layer.
The layer of an electronically insulating material, preferably an ionic conductor, should only be deposited on electrodes that do not contain an organic binder. In fact, the deposition by ALD is carried out at a temperature typically between 100 ° C. and 300 ° C. At this temperature, the organic materials forming the binder (for example the polymers contained in the electrodes produced by ink casting tape) risk decomposing and will pollute the ALD reactor. Furthermore, the presence of residual polymers in contact with the particles of electrode active material can prevent the ALD coating from coating all of the particle surfaces, which affects its effectiveness.
For example, an alumina layer with a thickness of about 1.6 nm may be suitable.
If the electrode is a cathode, it can be made from a cathode material P chosen from:
the oxides LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , LiMm.5Nio.5O4, LiMn ₁ , 5Ni _0.5 . _x XxO ₄ where X is selected from Al, Fe, Cr, Co, Rh, Nd, other rare earths such as Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho , Er, Tm, Yb, and where 0 <x <0.1, LiMn ₂ . _x M _x O ₄ with M = Er, Dy, Gd, Tb, Yb, Al, Y, Ni, Co, Ti, Sn, As, Mg or a mixture of these compounds and where 0 <x <0.4, LiFeO _2, LiMn _{1 /} 3Ni ₁ / 3Co _1/3 O _2, .UNi0.8Co0.15AI0.05O;>.
phosphates LiFePO ₄ , LiMnPO ₄ , LiCoPO ₄ , LiNiPO ₄ , Li ₃ V ₂ (PO ₄ ) ₃ ; phosphates of formula LiMM'PO ₄ , with M and M '(M + M') selected from Fe, Mn, Ni, Co, V;
- all the lithiated forms of the following chalcogenides: V ₂ O ₅ , V ₃ O ₈ , TiS ₂ , titanium oxysulfides (TiO _y S _z with z = 2-y and 0.3 <y <1), oxysulfides of tungsten (WO _y S _z with 0.6 <y <3 and 0.1 <z <2), CuS, CuS ₂ , preferably Li _x V ₂ O ₅ with 0 <x <2, Li _x V ₃ O ₈ with 0 <x <1.7, Li _x TiS ₂ with 0 <x <1, titanium and lithium oxysulfides Li _x TiO _y S _z with z = 2-y, 0.3 <y <1, Li _x WO _y S _z , Li _x CuS, Li _x CuS ₂ .
If the electrode is an anode, it can be made from an anode material P chosen from:
lithiated iron phosphate (of typical formula LiFePO ₄ );
mixed oxynitrides of silicon and tin (of typical formula Si _a Sn _b O _y N _z with a> 0, b> 0, a + b <2, 0 <y <4, 0 <z <3) (also called SiTON ), and in particular SiSn ₀ , 87Oi, 2N ₁ , 72; as well as the oxynitride-carbides of typical formula Si _a Sn _b C _c O _y N _z with a> 0, b> 0, a + b <2, 0 <c <10, 0 <y <24, 0 <z <17;
nitrides of type Si _x N _y (in particular with x = 3 and y = 4), Sn _x N _y (in particular with x = 3 and y = 4), Zn _x N _y (in particular with x = 3 and y = 2), Li ₃ . _x M _x N (with 0 <x <0.5 for M = Co, 0 <x <0.6 for M = Ni, 0 <x <0.3 for M = Cu); If ₃ . _x M _x N ₄ with 0 <x <3.
oxides SnO ₂ , SnO, Li ₂ SnO ₃ , SnSiO ₃ , LixSiOy (x> = 0 and 2>y> 0), Ι_ί ₄ Τί ₅ 0ΐ2, SnBo.ePo, 4 * 32.9 and T1O2.
On dense, porous, preferably mesoporous electrodes, whether or not coated with a layer of an electronically insulating material, preferably ionic conductor by ALD, an electrolyte according to the invention can be produced.
In order to obtain a battery with a high energy density and a high power density, this battery advantageously contains a layer of anode and a layer of porous cathode, preferably mesoporous, and an electrolyte according to the invention.
Advantageously, the anode and cathode layers, coated or not with an ALD layer of an electronically insulating material, preferably ionic conductor, then covered with an electrolyte layer according to the invention are hot pressed to favor the assembly of the cell.
In order to avoid the use of any liquid which could induce malfunctions, in particular the risk of fire of the battery, the production of a battery comprising dense electrodes and an electrolyte according to the invention will be preferred.
Advantageously, a battery comprising at least one porous, preferably mesoporous electrode and an electrolyte according to the invention has increased performance, in particular a high power density. We describe below an example of manufacture of a lithium ion battery according to the invention comprising at least one porous electrode, preferably mesoporous. This process includes the steps of:
(1) Supply of a colloidal suspension comprising nanoparticles of at least one cathode material of average primary diameter D ₅₀ less than or equal to 50 nm;
(2) Supply of a colloidal suspension comprising nanoparticles of at least one anode material with an average primary diameter D ₅₀ less than or equal to 50 nm;
(3) Supply of at least two flat, preferably metallic, conductive substrates, said conductive substrates being able to serve as battery current collectors, (4) Deposit of at least one thin layer of cathode, respectively anode, of preferably by dip-coating or by electrophoresis, preferably by galvanostatic electrodeposition by pulsed currents, from said suspension of nanoparticles of material obtained in step (1), respectively in step (2), on said substrate obtained in l step (3), (5) Drying of the layer thus obtained in step (4), (6) Optionally, deposition by ALD of a layer of an electronically insulating material on and inside the pores of the cathode and / or anode layer obtained in step (5), (7) Deposition by electrophoresis or by dip-coating of an electrolyte layer from a suspension of core-shell particles according to inventio n, on the cathode and / or anode layer obtained in step 5) or in step 6), to obtain a first and / or a second intermediate structure, (8) Drying of the layer thus obtained in step (7), preferably under an air flow, (9) Creation of a stack from said first and / or second intermediate structure to obtain a stack of the “substrate / anode / electrolyte / cathode” type / substrate ”:
• either by depositing an anode layer on said first intermediate structure, • or by depositing a cathode layer on said second intermediate structure, • or by superimposing said first intermediate structure and said second intermediate structure so that the two layers electrolyte are placed one on the other, (10) Hot pressing of the anode and cathode layers obtained in step (9) so as to assemble the films obtained in step (8) present on the anode and cathode layers, (11) Impregnation of the structure obtained in step (10) with a phase carrying lithium ions leading to the production of an impregnated structure, preferably a cell.
Once the assembly of a stack constituting a battery by hot pressing is complete, it can be impregnated with a phase carrying lithium ions. This phase can be a solution formed by a lithium salt dissolved in an organic solvent or a mixture of organic solvents, and / or dissolved in a polymer containing at least one lithium salt, and / or dissolved in an ionic liquid (ie a molten lithium salt) containing at least one lithium salt. This phase can also be a solution formed from a mixture of these components. The porous, preferably mesoporous, electrodes are capable of absorbing a liquid phase by simple capillarity when the mean diameter D ₅₀ of the pores is between 2 nm and 80 nm, preferably between 2 nm and 50 nm, preferably between 6 nm and 30 nm, preferably between 8 nm and 20 nm. This effect is completely unexpected and is particularly favored with the reduction in the pore diameters of these electrodes.
Advantageously, the pores of the porous electrode, preferably mesoporous, are impregnated with an electrolyte, preferably a phase carrying lithium ions such as an ionic liquid containing lithium salts, possibly diluted in an organic solvent or a mixture of organic solvents containing a lithium salt which may be different from that dissolved in the ionic liquid.
A lithium ion battery cell of very high power density is thus obtained.
4. Encapsulation
The battery must then be encapsulated by an appropriate method to ensure its protection from the atmosphere. The encapsulation system comprises at least one layer, and preferably represents a stack of several layers. If the encapsulation system consists of a single layer, it must be deposited by ALD or be made of parylene and / or polyimide. These encapsulation layers must be chemically stable, withstand high temperatures and be impermeable to the atmosphere (barrier layer). One of the methods described in patent applications WO 2017/115,032, WO 2016/001584, W02016 / 001588 or WO 2014/131997 can be used.
Advantageously, the first layer is a polymeric layer, preferably based on parylene and / or polyimide. It can be deposited under vacuum, by a chemical vapor deposition (CVD) technique. This first encapsulation layer is advantageously obtained from the condensation of gaseous monomers deposited by chemical vapor deposition (CVD) on the surfaces, which allows a conformai and uniform covering of all the accessible surfaces of the object. It makes it possible to follow the variations in volume of the battery during its operation and facilitates the clean cutting of the batteries due to its elastic properties. The thickness of this first encapsulation layer is between 2 μm and 10 μm, preferably between 2 μm and 5 μm and even more preferably around 3 μm. It makes it possible to cover all of the accessible surfaces of the stack, to close all of the pores of these accessible surfaces and to standardize the chemical nature of the substrate. The encapsulation can thus be carried out directly on the stacks, the coating being able to penetrate into all of the available cavities.
In one embodiment, a first layer of parylene is deposited, such as a layer of parylene C, of parylene D, a layer of parylene N (CAS No: 1633-22-3) or a layer comprising a mixture of parylene. C, D and / or N. Parylene (also called polyparaxylylene or poly (p-xylylene)) is a dielectric, transparent, semi-crystalline material which has high thermodynamic stability, excellent resistance to solvents and very low permeability .
This parylene layer protects the sensitive elements of the battery from their environment. This protection is increased when this first encapsulation layer is made from parylene N.
In another embodiment, a first layer based on polyimide is deposited. This polyimide layer protects the sensitive elements of the battery from their environment.
In another advantageous embodiment, the first encapsulation layer consists of a first layer of polyimide, preferably about 1 μm thick on which a second layer of parylene is deposited, preferably about 2 pm thick. This protection is increased when this second layer of parylene, preferably about 2 μm thick, is made from parylene N. The polyimide layer associated with the parylene layer improves the protection of the sensitive elements of the battery of their environment.
However, the inventors have observed that this first layer, when it is based on parylene, does not have sufficient stability in the presence of oxygen. When this first layer is based on polyimide, it does not have a sufficient seal, especially in the presence of water. For these reasons, a second layer is deposited which coats the first layer.
Advantageously, a second layer composed of an electrically insulating material can be deposited by a conformai deposition technique, such as the deposition of atomic layers (ALD) on the first layer. Thus a conformai covering is obtained of all the accessible surfaces of the stack covered with a layer of parylene and / or polyimide; this second layer is preferably an inorganic layer. The growth of the layer deposited by ALD is influenced by the nature of the substrate. A layer deposited by ALD on a substrate having different zones of different chemical natures will have an inhomogeneous growth, which can cause a loss of integrity of this second protective layer. This second layer deposited on the first layer of parylene and / or polyimide protects the first layer of parylene and / or polyimide against air and improves the life of the encapsulated battery.
The ALD deposition techniques are particularly well suited for covering surfaces with high roughness in a completely waterproof and conforming manner. They make it possible to produce conformal layers, free of defects, such as holes (so-called “pinhole free” layers, free of holes) and represent very good barriers. Their WVTR coefficient is extremely low. The WVTR (water vapor transmission rate) coefficient makes it possible to assess the water vapor permeance of the encapsulation system. The lower the WVTR coefficient, the more waterproof the encapsulation system. For example, a layer of AI ₂ O ₃ 100 nm thick deposited by ALD has a water vapor permeation of 0.00034 g / m ² .d. The second layer may be made of ceramic material, glassy material or glass-ceramic material, for example in the form of oxide, of the AI ₂ O _{3 type} , of nitride, of phosphates, of oxynitride, or of siloxane. This second encapsulation layer has a thickness of less than 200 nm, preferably between 5 nm and 200 nm, more preferably between 10 nm and 100 nm and even more preferably of the order of fifty nanometers.
This second layer deposited by ALD allows on the one hand, to ensure the tightness of the structure, ie to prevent the migration of water inside the structure and on the other hand to protect the first layer from parylene and / or polyimide from the atmosphere to avoid degradation.
However, these layers deposited by ALD are very fragile mechanically and require a rigid support surface to ensure their protective role. The deposition of a fragile layer on a flexible surface would lead to the formation of cracks, causing a loss of integrity of this protective layer.
In one embodiment, a third encapsulation layer is deposited on the second encapsulation layer to increase the protection of the battery cells from their external environment. Typically, this third layer is made of polymer, for example silicone (deposited for example by impregnation or by chemical vapor deposition assisted by plasma from hexamethyldisiloxane (HMDSO, CAS number: 10746-0)), or resin epoxy, or parylene, or polyimide.
In addition, the encapsulation system can comprise an alternating succession of layers of parylene and / or polyimide, preferably approximately 3 μm thick, and of layers composed of an electrically insulating material such as deposited inorganic layers. conformally by ALD as previously described to create a multi-layer encapsulation system. In order to improve the performance of the encapsulation, the encapsulation system can advantageously comprise a first layer of parylene and / or polyimide, preferably about 3 μm thick, a second layer composed of a material electrically insulating, preferably an inorganic layer, conformally deposited by ALD on the first layer, a third layer of parylene and / or polyimide, preferably about 3 μm thick deposited on the second layer and a fourth layer composed of an electrically insulating material conformally deposited by ALD on the third layer.
Advantageously, a last encapsulation layer is deposited on this alternating succession of parylene and / or polyimide layers, preferably about 3 μm thick and inorganic layers deposited conformally by ALD, to increase the protection of battery cells from their external environment and protect them from mechanical damage. This last encapsulation layer has a thickness of about 10-15 µm. Typically, this last layer is made of polymer, for example silicone (deposited for example by dipping or by chemical vapor deposition assisted by plasma from hexamethyldisiloxane (HMDSO)), or epoxy resin, or parylene, or polyimide. For example, it is possible to deposit by injection of a layer of silicone (typical thickness around 15 μm) to protect the battery against mechanical damage.
These materials resist high temperatures and the battery can thus be easily assembled by soldering on electronic cards without the appearance of a glass transition. Advantageously, the encapsulation of the battery is carried out on four of the six faces of the stack. The encapsulation layers surround the periphery of the stack, the rest of the protection against the atmosphere being provided by the layers obtained by the terminations.
After the battery encapsulation step, terminations are added to establish the electrical contacts necessary for the proper functioning of the battery.
To carry out the terminations, the encapsulated stack is cut along cutting planes making it possible to obtain unitary battery components, with the baring on each of the cutting planes of the anodic and cathodic connections of the battery, so that the encapsulation system covers four of the six faces of said battery, preferably continuously, so that the system can be assembled without welding, the other two faces of the battery being coated subsequently with the terminations. Preferably, the anode connections and the cathode connections are on the opposite sides of the stack. A termination system is placed on and around these connections. The connections can be metallized using plasma deposition techniques known to those skilled in the art, preferably by ALD and / or by immersion in a conductive epoxy resin (charged with silver) and / or a bath of molten tin. Preferably, the terminations consist of a stack of layers successively comprising a first thin layer of electronically conductive covering, preferably metallic, deposited by ALD, a second layer of silver-loaded epoxy resin deposited on the first layer and a third layer based on tin deposited on the second layer. The first conductive layer deposited by ALD is used to protect the section of the battery from humidity. This first conductive layer deposited by ALD is optional. It increases the calendar life of the battery by reducing the WVTR at the termination level. This first thin covering layer may in particular be metallic or based on metallic nitride. The second layer of epoxy resin loaded with silver, provides "flexibility" to the connectors without breaking the electrical contact when the electrical circuit is subjected to thermal and / or vibratory stresses.
The third layer of metallization based on tin is used to ensure the solderability of the battery.
In another embodiment, this third layer can be composed of two layers of different materials. A first layer coming into contact with the epoxy resin layer loaded with silver. This layer is made of nickel and is produced by electrolytic deposition. The nickel layer acts as a thermal barrier and protects the rest of the component from diffusion during the reflow assembly steps. The last layer, deposited on the nickel layer, is also a metallization layer, preferably made of tin to make the interface compatible with reflow assemblies. This layer of tin can be deposited either by soaking in a molten tin bath or by electrodeposition; these techniques are known as such.
For some assemblies on copper tracks by micro-wiring, it may be necessary to have a last layer of copper metallization. Such a layer can be produced by electrodeposition in place of tin.
In another embodiment, the terminations can consist of a stack of layers successively comprising a layer of epoxy resin loaded with silver and a second layer based on tin or nickel deposited on the first layer.
In another embodiment, the terminations may consist of a stack of layers successively comprising a layer of epoxy resin loaded with silver, a second layer based on nickel deposited on the first layer and a third layer based on tin or copper.
The terminations allow the alternating positive and negative electrical connections to be taken up at each end of the battery. These terminations allow electrical connections to be made in parallel between the various battery cells. For this, only the cathode connections exit on one end, and the anode connections are available on the other ends.
Examples
The examples below illustrate certain aspects of the invention but do not limit its scope.
Example 1: Manufacture of a layer of lithiated phosphate / PEO electrolyte
1. Preparation of a suspension of solid electrolyte nanoparticles coated with ion-conducting polymer
at. Production of a suspension of Li ₃ PO ₄ nanoparticles
Two solutions have been prepared:
11.44 g of CH ₃ COOLi, 2H ₂ O were dissolved in 112 ml of water, then 56 ml of water were added with vigorous stirring to the medium in order to obtain a solution A.
4.0584 g of H ₃ PO ₄ were diluted in 105.6 ml of water, then 45.6 ml of ethanol were added to this solution in order to obtain a second solution called hereinafter solution B.
Solution B was then added, with vigorous stirring, to solution A.
The solution obtained, perfectly clear after disappearance of the bubbles formed during mixing, was added to 1.2 liters of acetone under the action of a Ultraturrax ™ type homogenizer in order to homogenize the medium. White precipitation suspended in the liquid phase was immediately observed.
The reaction medium was homogenized for 5 minutes and then was kept for 10 minutes with magnetic stirring. Decanted for 1 to 2 hours. The supernatant was discarded and the remaining suspension was centrifuged for 10 minutes at 6000 rpm. Then 300 ml of water were added to resuspend the precipitate (use of a sonotrode, magnetic stirring). The colloidal suspension thus obtained comprises nanoparticles of Li ₃ PO ₄ at a concentration of 10 g / L.
b. Creation of a colloidal suspension of Li ₃ PO ₄ nanoparticles functionalized with PEO
The electrolyte nanoparticles previously obtained in suspension at a concentration of 10 g / L were then functionalized with methoxy-PE05000phosphonate (CAS: 911391-95-2 with n = 114).
An aqueous solution of this molecule was added to a colloidal suspension of electrolyte nanoparticles.
After adding this solution to the colloidal suspension of electrolyte nanoparticles, the reaction medium was left stirring for 1 hour at 70 ° C. so that the phosphonate groups are grafted onto the surface of the Li ₃ PO ₄ electrolyte nanoparticles. .
The nanoparticles thus functionalized were then purified by successive centrifugation and redispersion cycles so as to separate the functionalized particles from the unreacted molecules present in the supernatant. After centrifugation, the supernatant was removed. The pellet comprising the functionalized particles was redispersed in an amount of solvent making it possible to reach the desired dry extract.
2. Manufacture of an anode layer
A suspension of the anode material was prepared by grinding / dispersing a Li ₄ Ti ₅ O ₂ powder in absolute ethanol at about 10 g / L with a few ppm of citric acid. The grinding was carried out so as to obtain a stable suspension with a particle size D _{50 of} less than 70 nm.
An anode layer was deposited by electrophoresis of the Li ₄ Ti ₅ 0i2 nanoparticles contained in the suspension; this layer was deposited on both sides of a first conductive substrate with a thickness of 1 μm; it was dried and then heat treated at about 600 ° C. This anode layer was a so-called “dense” layer, having undergone a thermal consolidation step which leads to an increase in the density of the layer.
The anode was then coated with a protective coating of Li ₃ PO ₄ with a thickness of 10 nm deposited by ALD.
3. Making a cathode layer
A suspension was prepared at about 10 g / L of cathode material by grinding / dispersing a powder of LiMn ₂ O ₄ in water. Grinding of the suspension was carried out so as to obtain a stable suspension with a particle size D _{50 of} less than 50 nm.
A cathode was prepared by electrophoretic deposition of LiMn ₂ O ₄ nanoparticles contained in the suspension described above, in the form of a thin film deposited on both sides of a second conductive substrate; this cathode layer with a thickness of 1 μm was then heat treated at approximately 600 ° C. This cathode layer was a so-called “dense” layer, having undergone a thermal consolidation step which leads to an increase in the density of the layer.
The cathode was then coated with a protective coating of Li ₃ PO ₄ with a thickness of 10 nm deposited by ALD.
4. Manufacture of a layer of lithiated phosphate / PEO electrolyte
The nanoparticles in suspension thus functionalized were deposited by electrophoresis on the first (respectively second) conductive substrate previously covered with an anode layer as indicated previously in point 2 of the example above, respectively of cathode as indicated previously in point 3 of the example above, by applying between the substrate and a counter electrode, both immersed in the colloidal suspension, a voltage of 45 V until a layer of 1.4 μm in thickness is obtained.
The layer thus obtained was dried.
5. Manufacture of a battery comprising an electrolyte according to the invention
The anode obtained in Example 1.2 and the cathode obtained in Example 1.3 were stacked on their electrolyte faces and the assembly was kept under pressure at 50 MPa for 15 minutes at 200 ° C; a lithium ion battery was thus obtained which could be charged and discharged in numerous cycles.

权利要求:
Claims (1)
[1" id="c-fr-0001]
Method for manufacturing an electrolyte, preferably in a thin layer, for a lithium ion battery or supercapacitor, deposited on an electrode, comprising the steps of:
at. supply of a conductive substrate, previously covered with a layer of a material which can serve as an electrode ("electrode layer"),
b. deposition on said electrode layer of an electrolyte layer, preferably by electrophoresis or by dip-coating, from a suspension of core-shell particles comprising as core, a particle of a material which can be used as an electrolyte or of electronic insulator, on which is grafted a bark comprising PEO;
vs. Drying of the electrolyte layer thus obtained, preferably under an air flow;
d. optionally, densification of said electrolyte layer by mechanical compression and / or heat treatment.
Process according to Claim 1, in which the mean size D ₅₀ of the primary primary particles is less than 100 nm, preferably less than 50 nm and even more preferably less than or equal to 30 nm.
The method of claim 1 or 2, wherein said core particles are obtained by hydrothermal or solvothermal synthesis.
Process according to any one of Claims 1 to 3, in which the thickness of the shell of the core-shell particles is between 1 nm and 100 nm.
Method according to any one of claims 1 to 4, in which the electrolyte layer obtained in step c) or d) has a thickness of less than 5 µm, preferably about 3 µm.
The process according to any of claims 1 to 5, wherein the PEO has a weight average molecular weight of less than 7000 g / mol, preferably about 5000 g / mol.
7. Method according to any one of claims 1 to 6, wherein the dry extract of the suspension of core-shell particles used in step b) is less than 30% by mass.
8. Use of a method according to any one of claims 1 to 7 for the manufacture of electrolytes, preferably in a thin layer, in electronic, electrical or electrotechnical devices, and preferably in devices selected from the group formed by: batteries, capacitors, supercapacitors, capacitors, resistors, inductors, transistors.
9. Electrolyte, preferably in a thin layer, capable of being obtained by the method according to any one of claims 1 to 7.
10. Electrolyte, preferably in a thin layer, according to claim 9, comprising a solid electrolyte and PEO, characterized in that it has a solid electrolyte / PEO volume ratio greater than 35%, preferably greater than 50%, preferably greater than 60%, and even more preferably greater than 70%.
11. Electrolyte, preferably in a thin layer, according to claim 9 or 10, characterized in that it has a porosity of less than 20%, preferably less than 15%, even more preferably less than 10%.
12. An electrochemical device comprising at least one electrolyte, preferably in a thin layer, according to any one of claims 9 or 10 or 11, preferably a lithium ion battery or a supercapacitor.
13. A method of manufacturing a lithium ion battery implementing the method according to any one of claims 1 to 7, and comprising the steps of:
i. Supply of at least two conductive substrates which can serve as battery current collectors, previously covered with a layer of a material which can serve as an anode and respectively as a cathode (“anode layer” respectively “cathode layer”), and being covered on at least part of at least one of their faces with a layer of cathode, respectively of anode, iii.
iv.
v.
vi.
Supply of a colloidal suspension comprising core-shell nanoparticles comprising as core, a particle of a material which can be used as an electrolyte or electronic insulator, onto which a shell comprising PEO is grafted,
Deposition of an electrolyte layer, preferably by electrophoresis or by dip-coating, from a suspension of core-shell particles obtained in step ii), on the cathode layer, and / or anode obtained in step i), to obtain a first and / or a second intermediate structure, drying of the layer thus obtained in step iii), preferably under an air flow,
Realization of a stack from said first and / or second intermediate structure to obtain a stack of the “substrate / anode / electrolyte / cathode / substrate” type:
• either by depositing an anode layer on said first intermediate structure, • or by depositing a cathode layer on said second intermediate structure, • or by superimposing said first intermediate structure and said second intermediate structure so that the two layers of electrolyte are placed one on the other,
Densification of the stack obtained in the previous step by mechanical compression and / or heat treatment of the stack leading to the production of a battery.
14. The method of claim 13, wherein the cathode is a dense electrode or a dense electrode coated with ALD with an electronically insulating layer, preferably an electronically insulating and ionically conductive layer, or a porous electrode, or a porous electrode coated by ALD with an electronically insulating layer, preferably with an electronically insulating and ionically conductive layer, or, preferably, a mesoporous electrode, or a mesoporous electrode coated with ALD with an electronically insulating layer, preferably with an an electronically insulating and ionically conductive layer, and / or in which the anode is a dense electrode or a dense electrode coated by ALD with an electronically insulating layer, preferably an electronically insulating and ionic conductive layer, or an electrode porous, or a porous electrode coated by ALD with an electronic insulating layer uement, preferably an electronically insulating and ionically conductive layer, or preferably a mesoporous electrode, or a mesoporous electrode coated with ALD with an electronically insulating layer, preferably an electronically insulating and ionic conductive layer.
15. Method according to any one of claims 13 to 14, in which after step vi):
- successively, alternately, depositing on the battery:
o at least a first layer of parylene and / or polyimide on said battery, o at least a second layer composed of an electrically insulating material by ALD (Atomic Layer Deposition) on said first layer of parylene and / or polyimide, o and on the alternating succession of at least a first and at least a second layer is deposited a layer making it possible to protect the battery against mechanical damage to the battery, preferably made of silicone, epoxy resin or parylene, thus forming, a battery encapsulation system, the battery thus encapsulated is cut along two cutting planes in order to expose anode and cathode connections of the battery on each of the section planes, so that the encapsulation system takes four of the six faces of said battery, preferably continuously, these anodic and cathodic connections are deposited successively, on and around:
o an optional first electronically conductive layer, preferably deposited by ALD, o a second layer based on silver-charged epoxy resin, deposited on the first electronically conductive layer, and o a third layer based on nickel, deposited on the second layer, and
16.
17.
o a fourth layer based on tin or copper, deposited on the third layer.
The method of claim 15, wherein the anode and cathode connections are on opposite sides of the stack.
Lithium ion battery obtainable by the method according to any of claims 13 to 16.

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同族专利:

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公开号 | 公开日

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JP2021522661A|2021-08-30|

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SG11202010867QA|2020-12-30|

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CN112042031A|2020-12-04|

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法律状态:
2019-05-24| PLFP| Fee payment|Year of fee payment: 2 |

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2019-11-08| PLSC| Search report ready|Effective date: 20191108 |

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优先权:

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申请号 | 申请日 | 专利标题

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FR1853923|2018-05-07|

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FR1853923A|FR3080952B1|2018-05-07|2018-05-07|ELECTROLYTE FOR THIN FILM ELECTROCHEMICAL DEVICES|FR1853923A| FR3080952B1|2018-05-07|2018-05-07|ELECTROLYTE FOR THIN FILM ELECTROCHEMICAL DEVICES|

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SG11202010867QA| SG11202010867QA|2018-05-07|2019-05-06|Solid electrolyte for electrochemical devices|

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US17/049,983| US20210104777A1|2018-05-07|2019-05-06|Solid electrolyte for electrochemical devices|

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EP19728502.6A| EP3766119A1|2018-05-07|2019-05-06|Solid electroyte for electrochemical devices|

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CA3098637A| CA3098637A1|2018-05-07|2019-05-06|Solid electroyte for electrochemical devices|

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CN201980029320.0A| CN112042031A|2018-05-07|2019-05-06|Solid electrolyte for electrochemical device|

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JP2020560766A| JP2021522661A|2018-05-07|2019-05-06|Solid electrolytes for electrochemical devices|

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PCT/FR2019/051032| WO2019215410A1|2018-05-07|2019-05-06|Solid electroyte for electrochemical devices|