CN117897822A

CN117897822A - High power density and low cost lithium ion battery

Info

Publication number: CN117897822A
Application number: CN202280047243.3A
Authority: CN
Inventors: 法比安·加邦
Original assignee: I Ten SA
Current assignee: I Ten SA
Priority date: 2021-06-30
Filing date: 2022-06-29
Publication date: 2024-04-16

Abstract

Lithium ion battery comprising at least one stack, said stack comprising in sequence: a first electronic current collector, a first porous electrode, a porous separator, a second porous electrode, and a second electronic current collector, the first porous electrode being made of a material selected from the group consisting of: nb (Nb) _2‑x M ¹ _x O _5‑δ M ³ ，Nb _18‑x M ¹ _x W _16‑y M ² _y O _93‑δ M ³ ，Nb _16‑ _x M ¹ _x W _5‑y M ² _y O _55‑δ M ³ ，Nb ₂ O _5‑δ Wherein delta is more than or equal to 0 and less than or equal to 2, nb ₁₈ W ₁₆ O _93‑δ Wherein delta is more than or equal to 0 and less than or equal to 2, nb ₁₆ W ₅ O _55‑δ Wherein delta is more than or equal to 0 and less than or equal to 2, li is ₄ Ti ₅ O ₁₂ And Li (lithium) ₄ Ti _5‑x M _x O ₁₂ Wherein m= V, zr, hf, nb, ta and 0+.x+.0.25, the porous separator is made of an electrically insulating inorganic material, the second porous electrode is made of phosphate or lithium oxide, wherein the electrolyte of the battery is a liquid filled with lithium ions sealed in porous layers, each of the three porous layers being binder free and having a porosity of 20 to 70% by volume.

Description

High power density and low cost lithium ion battery

Technical Field

The present invention relates to the field of electrochemical systems for storing electrical energy, and more particularly to the field of lithium ion batteries. The present invention relates to a novel battery which has a high power density, good stability and can be used in a very wide temperature range (below-20 and above +85 ). It has a porous electrode, a material of particular choice. It also allows for fast charging. It can be manufactured at low cost, which is in part related to the relatively low cost of raw materials used to manufacture the electrode.

Background

The electronics industry requires secondary batteries of different forms, different uses and different specifications. Secondary micro-batteries are particularly desirable, for example, to ensure a clock backup function, a power-down protection function of a memory, or an energy buffer storage function of an autonomous sensor, a smart card, and an RFID tag. In fact, these electronic devices often comprise electrical energy generating sources based on different technologies for capturing the surrounding energy. These may be, for example, photocells or rectenna for converting electromagnetic waves into electric current, or thermopiles.

However, all of these energy production sources are not very powerful and their operation depends on their environment. Furthermore, in order to ensure the operation of the device, it must be possible to store this energy reliably and to save it after it has been generated until the electronics need it to perform a specific function, which may be for example to transmit a signal or to perform a calculation. These specific communication functions and the like generally require a high current in a short time. For example, to communicate over a network, electronics may require tens of milliamps of current for hundreds of milliseconds. The capacity of such microbatteries is typically about 10 mu A.h to about 0.5ma.h. In complex circuits, batteries with higher capacities than 1ma.h may be preferred, especially for applications in 5G type mobile communication protocols.

Furthermore, the sensor or other electronics are typically placed outdoors and must be capable of operating over a very wide temperature range, typically ranging from-40 to +85 . To date, there are no electronic components capable of performing all of these functions. In order for batteries (batteries) and cells to be able to deliver the required current, their capacity must be relatively high, on the order of tens or hundreds of mAh. These are essentially button cells or mini cells. For supercapacitors, due to their low volumetric energy density, they are very heavy and self-discharge is severe.

The present invention aims to produce a battery, in particular a micro battery, in the form of an electronic component which can be surface mounted (surface mounted component, SMD) on an electronic circuit and assembled by reflow soldering, and which allows storing a large amount of energy with a small space required to meet the miniaturization requirements of the electronic industry. To ensure miniaturization, the microbattery according to the invention must combine the characteristics of batteries and supercapacitors.

In fact, the current that a battery can provide is proportional to its capacity. With the current technology, micro-cells with a capacity of tens or even hundreds of ah are difficult to deliver a current of tens of mA. In fact, for rechargeable lithium ion batteries where power is greatest, their current density is about 10 to 50C. In other words, the ratio of power P to energy E (P/E ratio) is 10, and a battery capable of providing 10C must have a capacity of 5mAh to provide a current of 50 mA.

Thus, the battery available to power the autonomous sensor must have a capacity of a few mAh in order to be able to power the communication transients of the autonomous sensor. Thus, they are not just micro-batteries, but also mini-batteries, button cells or SMD components. The battery according to the invention allows to ensure the operation of all the connected objects by virtue of its high performance, lifetime and autonomy. The mini-battery can especially meet the energy requirements of any internet of things telecommunication protocol. The micro-battery allows to meet the low energy requirements of any communication protocol between machines, abbreviated as M2M (machine to machine), especially in low power extension networks such as bluetooth, loraWan, zigbee networks, which are designed to facilitate long distance communication between sensors and other connected devices at low data rates.

On the other hand, although lithium ion batteries meet the self-discharge requirements, their operating temperature range is still very limited. Lithium ion batteries using solvent-based liquid electrolytes and graphite anodes can only operate at temperatures around 60 . When this temperature is exceeded, they rapidly degrade; such degradation can lead to thermal runaway and explosion of the battery.

The automotive industry expresses another urgent need for a low cost compact battery with very high power density even at low temperatures and with excellent cycle life. More specifically, batteries having these characteristics are particularly required for use in hybrid vehicles equipped with an internal combustion engine and an electric motor; this need is enhanced in the context of a technique known as "micro-mixing" or "light mixing". The cost of a battery, particularly for an electric vehicle, is essentially related to the price of the raw materials that make up the active material. In order to achieve the cost goals of the automotive industry, it is therefore necessary to have inexpensive and large amounts of available battery materials. For example, the battery sales price of a "mild hybrid" vehicle must not exceed around $100 per kWh. If this cost problem is solved, it is also possible to consider the use of these batteries in other electric vehicles (electric bicycles, electric scooters, electric pedals) and other mobile devices (for example electric tools) or stationary electric energy storage facilities.

For this type of battery, one of the most suitable architectures is a battery consisting of an anode selected from the group consisting of:

Nb ₂ O _5- wherein delta is more than or equal to 0 and less than or equal to 2,

Nb ₁₈ W ₁₆ O _93- wherein delta is more than or equal to 0 and less than or equal to 2,

Nb _2-x M ¹ _x O _5- M ³ wherein the method comprises the steps of

M ¹ Is at least one element selected from the group consisting of: nb, V, ta, fe, co, ti, bi, sb, as, P, cr, mo, W, B, na, mg, ca, ba, pb, al, zr, si, sr, K, ge, ce, cs and Sn;

M ³ at least one halogen, preferably selected from F, cl, br, I or mixtures thereof

And wherein 0.ltoreq.x.ltoreq.1 and 0.ltoreq.delta.ltoreq.2,

Nb _18-x M ¹ _x W _16-y M ² _y O _93- M ³ wherein

M ¹ And M ² Is selected from the group consisting ofAt least one element of the group: nb, V, ta, fe, co, ti, bi, sb, as, P, cr, mo, W, B, na, mg, ca, ba, pb, al, zr, si, sr, K, ge, ce, cs and Sn;

M ¹ and M ² May be the same as or different from each other,

M ³ is at least one halogen, preferably selected from F, cl, br, I or a mixture thereof,

and wherein 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.2 and 0.ltoreq.delta.ltoreq.2,

Nb _16-x M ¹ _x W _5-y M ² _y O _55- M ³ wherein

M ¹ And M ² Is at least one element selected from the group consisting of: nb, V, ta, fe, co, ti, bi, sb, as, P, cr, mo, W, B, na, mg, ca, ba, pb, al, zr, si, sr, K, ge, ce, cs and Sn;

M ¹ And M ² May be the same as or different from each other,

-Nb ₁₆ W ₅ O _55- wherein delta is more than or equal to 0 and less than or equal to 2,

-Li ₄ Ti ₅ O ₁₂ or TiNb ₂ O ₇

-cathode LiMn ₂ O ₄ And/or LiFePO ₄

In fact, these materials contain little or no precious, expensive or rare metallic elements and are inexpensive to synthesize. In addition, li ₄ Ti ₅ O ₁₂ And TiNb ₂ O ₇ Operating at high potential, they are compatible with fast charging and have excellent cycle performance.

Compounds of formula (I)

-Nb _2-x M ¹ _x O _5- M ³ Wherein the method comprises the steps of

-M ¹ Is at least one element selected from the group consisting of: nb, V, ta, fe, co, ti, bi, sb, as, P, cr, mo, W, B, na, mg, ca, ba, pb, al, zr, si, sr, K, ge, ce, cs and Sn;

-M ³ at least one halogen, preferably selected from F, cl, br, I or mixtures thereof

And wherein 0.ltoreq.x.ltoreq.1 and 0.ltoreq.delta.ltoreq.2,

-Nb _18-x M ¹ _x W _16-y M ² _y O _93- M ³ wherein

M ¹ and M ² May be the same as or different from each other,

-Nb _16-x M ¹ _x W _5-y M ² _y O _55- M ³ wherein

M ¹ and M ² May be the same as or different from each other,

-Nb ₂ O _5- wherein delta is more than or equal to 0 and less than or equal to 2,

-Nb ₁₈ W ₁₆ O _93- wherein 0.ltoreq.2Delta is less than or equal to 2, and/or

-Nb ₁₆ W ₅ O _55- Wherein 0.ltoreq.delta.ltoreq.2, may be used to form anodes compatible with fast recharging.

However, there are still difficulties to be solved in order to be able to use such architecture in automotive and/or stationary applications. One of these difficulties is related to power density: the applications considered require batteries capable of delivering high currents at very low temperatures (about-30 ), which is not satisfactory in the lithium-ion batteries according to the prior art.

Furthermore, the cycle life of such batteries must be on the order of hundreds of thousands of charge and discharge cycles. The lithium ion battery in the prior art cannot achieve the purpose. In fact, as the cycle proceeds, electrical contact between the active material particles may be lost, thereby reducing the capacity of the battery.

Regarding the above-mentioned low-cost battery material, liFePO which can be used as a cathode material ₄ Has a relatively high electrical resistance and it has proven to be very difficult to achieve very high power cell architectures and high energy densities with this type of material. With respect to LiMn ₂ O ₄ A further problem is its high temperature stability in aprotic solvents. In fact, above 55Mn ²⁺ Ions are dissolved in most electrolytes, resulting in a significant decrease in battery performance.

Furthermore, it is an object of the present invention to produce a battery that can have a capacity from a few percent mAh to tens of Ah, capable of delivering high currents. Thus, a battery (battery) according to the present invention may be a single battery (cell), i.e., a battery (battery) comprising a single battery, referred to as a "battery cell", or a battery (battery) comprising a plurality of batteries (cells), also referred to as a "battery system". The battery according to the invention may also be:

-a battery with a capacity greater than 1mAh, or

Microcells, i.e. batteries having a capacity of not more than 1mA h, for example in the form of button cells or SMD components.

In particular, the invention allows the production of micro-batteries with very low capacities, meeting the miniaturization requirements of the electronic industry, and being able to deliver high currents. Such microbatteries must be able to operate at very low temperatures: outdoor electronics applications require operating temperatures as low as-40 , but the electrolyte of conventional lithium ion batteries freezes at temperatures approaching-20 . These outdoor applications also require operation at high temperatures, which can reach temperatures even exceeding +85, without any risk of fire.

Furthermore, the profile of such a battery must be of the type of SMD component standard in the electronic industry in order to be able to be automatically mounted on pick and place and reflow type assembly lines. In the case of a mini-cell, the element may be in the form of a button cell or a through-hole element.

Such a battery should also have an excellent cycle life to extend the useful life of the discarded sensors and limit maintenance costs associated with premature aging of the battery.

Finally, in the special case of smart cards, the element must be equipped with extremely fast recharging capability in order to be able to harvest the maximum energy during the extremely fast recharging transients encountered during contactless payment.

The present invention also aims to provide a battery with a capacity greater than 1mAh, capable of being recharged very rapidly from a large part of its nominal capacity, and capable of operating at very low temperatures: vehicles must be able to operate outdoors at temperatures as low as around-30 (electrolytes of conventional lithium ion batteries are known to freeze at temperatures fairly close to-20 ). These outdoor applications also require operation at high temperatures, which can reach temperatures even exceeding +85, without any risk of fire.

Such a battery must also have an excellent cycle life and must be able to recharge very quickly from a significant portion of its nominal capacity without shortening its life in order to be able to obtain maximum energy, for example, when occasionally parked on a highway service.

Disclosure of Invention

According to the invention, this problem is solved by a method and a battery incorporating a certain number of devices.

A first object of the invention is a lithium-ion battery, preferably selected from micro-batteries having a capacity of not more than 1mA h and batteries having a capacity of more than 1mA h, comprising at least one stack comprising, in order: a first electronic current collector, a first porous electrode, a first porous separator, a second porous electrode, and a second electronic current collector, the electrolyte of the battery being known to be a liquid filled with lithium ions confined in the porous layer, the battery being characterized in that:

-said first electrode is an anode comprising a porous layer made of a material PA selected from the group consisting of:

Nb _2-x M ¹ _x O _5- M ³ wherein

And wherein 0.ltoreq.x.ltoreq.1 and 0.ltoreq.delta.ltoreq.2,

Nb _18-x M ¹ _x W _16-y M ² _y O _93- M ³ wherein

M ¹ and M ² May be the same as or different from each other,

And wherein x is 0.ltoreq.1, y is 0.ltoreq.2 and delta is 0.ltoreq.2,

Nb _16-x M ¹ _x W _5-y M ² _y O _55- M ³ wherein

M ¹ and M ² May be the same as or different from each other,

And wherein x is 0.ltoreq.1, y is 0.ltoreq.2 and delta is 0.ltoreq.2,

Nb ₂ O _5- wherein delta is more than or equal to 0 and less than or equal to 2, nb ₁₈ W ₁₆ O _93- Wherein delta is more than or equal to 0 and less than or equal to 2, nb ₁₆ W ₅ O _55- Wherein delta is more than or equal to 0 and less than or equal to 2, li is ₄ Ti ₅ O ₁₂ And Li (lithium) ₄ Ti _5-x M _x O ₁₂ Wherein m= V, zr, hf, nb, ta and 0.ltoreq.x.ltoreq.0.25 and wherein part of the oxygen atoms may be substituted by halogen atoms and/or may be doped by halogen atoms, and the layer is binder-free, has a porosity of 20 to 70% by volume, preferably 25 to 65% by volume, even more preferably 30 to 60% by volume,

-said separator comprises a porous inorganic layer made of an electrically insulating inorganic material E, preferably selected from:

Al ₂ O ₃ SiO ₂ ZrO ₂ a kind of electronic device

Material selected from: lithiated phosphate optionally containing at least one element selected from the group consisting of: al, ca, B, Y, sc, ga, zr; or lithiated borates, which may optionally contain at least one element from the group consisting of: al, ca, Y, sc, ga, zr; the material is preferably selected from: naSICON type lithiated phosphate, li ₃ PO ₄ LiPO ₃ Li ₃ Al _0.4 Sc _1.6 (PO ₄ ) ₃ Called "LASP"; li (Li) _1+x Zr _2-x Ca _x (PO ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 0.25; li (Li) _1+2x Zr _2-x Ca _x (PO ₄ ) ₃ Which is provided withWherein 0.ltoreq.x.ltoreq.0.25, e.g. Li _1.2 Zr _1.9 Ca _0.1 (PO ₄ ) ₃ Or Li (lithium) _1.4 Zr _1.8 Ca _0.2 (PO ₄ ) ₃ LiZr ₂ (PO ₄ ) ₃ Li _1+3x Zr ₂ (P _1-x Si _x O ₄ ) ₃ 1.8 of<x<2.3Li _1+6x Zr ₂ (P _1-x B _x O ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 0.25; li (Li) ₃ (Sc _2-x M _x )(PO ₄ ) ₃ Wherein M=Al or Y and 0.ltoreq.x.ltoreq.1; li (Li) _1+x M _x (Sc) _2-x (PO ₄ ) ₃ Wherein m=al, Y, ga or a mixture of these three elements, and 0.ltoreq.x.ltoreq.0.8; li (Li) _1+x M _x (Ga _1- _y Sc _y ) _2-x (PO ₄ ) ₃ Wherein 0.ltoreq.x.ltoreq.0.8, 0.ltoreq.y.ltoreq.1 and M=Al and/or Y; li (Li) _1+x M _x (Ga) _2-x (PO ₄ ) ₃ Wherein M=Al and/or Y and 0.ltoreq.x.ltoreq.0.8; li (Li) _1+x Al _x Ti _2-x (PO ₄ ) ₃ Wherein 0.ltoreq.x.ltoreq.1, called "LATP"; or Li (lithium) _1+x Al _x Ge _2-x (PO ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 1 is called as 'LAGP'; or Li (lithium) _1+x+z M _x (Ge _1-y Ti _y ) _2-x Si _z P _3-z O ₁₂ Wherein 0.ltoreq.x.ltoreq.0.8 and 0.ltoreq.y.ltoreq.1.0 and 0.ltoreq.z.ltoreq.0.6 and M=Al, ga or Y or a mixture of two or three of these elements; li (Li) _3+y (Sc _2-x M _x )Q _y P _3-y O ₁₂ Wherein m=al and/or Y and q=si and/or Se, 0.ltoreq.x.ltoreq.0.8 and 0.ltoreq.y.ltoreq.1; or Li (lithium) _1+x+y M _x Sc _2-x Q _y P _3-y O ₁₂ Wherein m=al, Y, ga or a mixture of these three elements and q=si and/or Se, 0.ltoreq.x.ltoreq.0.8 and 0.ltoreq.y.ltoreq.1; or Li (lithium) _1+x+y+z M _x (Ga _1- _y Sc _y ) _2-x Q _z P _3-z O ₁₂ Wherein 0.ltoreq.x.ltoreq.0.8, 0.ltoreq.y.ltoreq.1 and 0.ltoreq.z.ltoreq.0.6, wherein m=al and/or Y and q=si and/or Se; or Li (lithium) _1+x Zr _2-x B _x (PO ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 0.25; or Li (lithium) _1+x M ³ _x M _2-x P ₃ O ₁₂ Wherein 0.ltoreq.x.ltoreq.1 and M ³ Cr, V, ca, B, mg, bi and/or Mo, m= Sc, sn, zr, hf, se or Si, or mixtures of these elements;

the porous layer is binder-free and has a porosity of 20 to 70% by volume, preferably 25 to 65% by volume, even more preferably 30 to 60% by volume;

-the second electrode is a cathode comprising a porous layer made of material PC selected from the group consisting of:

-LiFePO ₄

-LiFeMPO ₄ Wherein M is selected from the group consisting of Mn, ni, co, V,

-oxide LiMn ₂ O ₄ Li _1+x Mn _2-x O ₄ Wherein 0 is<x<0.15LiCoO ₂ LiNiO ₂ LiMn _1.5 Ni _0.5 O ₄ LiMn _1.5 Ni _0.5-x X _x O ₄ Wherein X is selected from Al, fe, cr, co, rh, nd, other rare earth metal elements such as Sc, Y, lu, la, ce, pr, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, and wherein 0<x<0.1LiMn _2-x M _x O ₄ Wherein m= Er, dy, gd, tb, yb, al, Y, ni, co, ti, sn, as, mg or a mixture of these compounds, and wherein 0<x<0.4LiFeO ₂ LiMn _1/3 Ni _1/ ₃ Co _1/3 O ₂ LiNi _0.8 Co _0.15 Al _0.05 O ₂ LiAl _x Mn _2-x O ₄ Wherein 0.ltoreq.x<0.15LiNi _1/x Co _1/y Mn _1/z O ₂ Wherein x+y+z=10;

-oxide Li _x M _y O ₂ Wherein 0.6.ltoreq.y.ltoreq.0.85 and 0.ltoreq.x+y.ltoreq.2, and M is selected from Al, ti, cr, mn, fe, co, ni, cu, zn, zr, nb, mo, ru, sn and Sb or mixtures of these elements; li (Li) _1.20 Nb _0.20 Mn _0.60 O ₂

-Li _1+x Nb _y Me _z A _p O ₂ Wherein a and Me are each at least one transition metal selected from the group consisting of: sc, ti, V, cr, mn, fe, co, ni, cu, zn, Y, zr, nb, mo, tc, ru, rh, pd, ag, cd, hf, ta, W, re, os, ir, pt, au, hg, and 0.6 therein<x<10<y<0.50.25z<1, a step of; wherein A is not equal to Me, A is not equal to Nb, and p is not less than 0 and not more than 0.2;

-Li _x Nb _y-a N _a M _z-b P _b O _2-c F _c 1.2 therein<x1.750y<0.550.1<z<10a<0.50b<.10c<0.8; and wherein M, N, and P are each at least one element selected from the group consisting of: ti, ta, V, cr, mn, fe, co, ni, cu, zn, al, zr, Y, mo, ru, rh, and Sb;

-oxide Li _1.25 Nb _0.25 Mn _0.50 O ₂ Li _1.3 Nb _0.3 Mn _0.40 O ₂ Li _1.3 Nb _0.3 Fe _0.40 O ₂ Li _1.3 Nb _0.43 Ni _0.27 O ₂ Li _1.3 Nb _0.43 Co _0.27 O ₂ Li _1.4 Nb _0.2 Mn _0.53 O ₂

-oxide Li _x Ni _0.2 Mn _0.6 O _y Wherein x is more than or equal to 0.00 and less than or equal to 1.52; y is more than or equal to 1.07<2.4Li _1.2 Ni _0.2 Mn _0.6 O ₂

-Compound Li _1.9 Mn _0.95 O _2.05 F _0.95 LiVPO ₄ FFeF ₃ FeF ₂ CoF ₂ CuF ₂ NiF ₂ Fe _1-x M _x OF 0<x<0.2 and M is at least one element selected from the group consisting of Co, ni, mn and Cu,

oxide LiNi _x Co _y Mn _1-x-y O ₂ Wherein 0.ltoreq.x and y.ltoreq.0.5; liNi _x Ce _z Co _y Mn _1-x-y O ₂ Wherein 0.ltoreq.x and y.ltoreq.0.5 and 0.ltoreq.z,

the porous layer is binder-free and has a porosity of 20 to 70% by volume, preferably 25 to 65% by volume, even more preferably 30 to 60% by volume, and the separator comprises a porous inorganic layer deposited on the first and/or second electrode, the porous inorganic layer being binder-free and having a porosity of 20 to 70% by volume, preferably 25 to 65% by volume, even more preferably 30 to 60% by volume.

The combined use of a porous structure, an all-ceramic structure without organic binder, an ionic liquid-based electrolyte (which can be used only due to the all-ceramic structure), a corrosion resistant substrate, and an electronically conductive coating on the inner surface of the electrode (more specifically the cathode) for electrodes exceeding a certain thickness can result in an extremely reliable battery that can operate at-40 to +125 even though the crystallization temperature of the liquid electrolyte is higher than-40 . The use of the battery according to the invention at temperatures below-10 and/or above +80 is a further object of the invention.

For lithium ion batteries, the expression "fully ceramic structure" is used herein to mean that the solid phase of the battery no longer comprises organic residues; any binders, additives or organic solvents used during the process of depositing the layers forming the cell (all of which are eliminated by pyrolysis). The liquid electrolyte may comprise organic materials, in particular organic liquids and optionally solvents for diluting them.

This property of the battery obtained by the method according to the invention is related to the fact that no separator and organic binder are present anymore. The battery combines the extended operating temperature range with a power density that is extraordinary in comparison to its power density. It does not present a safety risk, the battery does not catch fire, and it can be charged extremely quickly.

This property is also related to the choice of material. The applicant has appreciated that when the battery is operated at temperatures above about 50 to 60 , a cathode containing manganese oxide cannot guarantee long-term operation at high temperatures, as manganese may be dissolved in common liquid electrolytes based on aprotic solvents.

According to a basic feature of the invention, the electrode layer and the separator layer are porous. More specifically, they comprise an open porous network. According to a first embodiment, the pores are mesopores and their average diameter is smaller than 50nm, preferably 10nm to 50nm, more preferably 20nm to 50nm. The layers may be obtained from colloidal suspensions comprising aggregates or agglomerates of monodisperse primary particles, the average primary diameter D of the nanoparticles ₅₀ From 2nm to 100nm, preferably from 2nm to 60nm, the average diameter D of the aggregates or agglomerates ₅₀ 50nm to 300nm, preferably 100nm to 200nm. According to a second embodiment, the average diameter of the pores is greater than 50nm, more particularly greater than 100nm. These layers can be obtained from colloidal suspensions comprising non-agglomerated or non-aggregated primary particles, the average diameter D of the primary particles ₅₀ 200nm to 10. Mu.m, preferably 300nm to 5. Mu.m; the particle size distribution of these particles should be quite narrow. The uniform size of the particles facilitates their consolidation and results in uniform pore size.

When the thickness of the electrode layer exceeds about 5 m to 10 m, it is particularly advantageous to deposit a thin layer of a material having excellent electron conductivity, preferably metallic conductivity, within the porous network; such material may be graphitic carbon or an electronically conductive oxide material. Such a coating is not necessary when the thickness of the electrode is only a few microns; in any event, it improves the power performance of the battery.

Another object of the invention is a method for manufacturing a lithium ion battery, preferably selected from micro-batteries having a capacity of not more than 1mAh or batteries having a capacity of more than 1mAh, said battery comprising at least one stack comprising, in sequence: a first electronic current collector, a first porous electrode, a first porous separator, a second porous electrode, and a second electronic current collector, the electrolyte of the battery being known to be a liquid filled with lithium ions confined in the porous layer;

the manufacturing method implements a method for manufacturing an assembly comprising a first porous electrode and a porous separator,

the first electrode comprises a porous layer deposited on a substrate, the layer being binder-free and having a porosity of 20 to 70% by volume, preferably 25 to 65% by volume, even more preferably 30 to 60% by volume, the separator comprising a porous inorganic layer deposited on the electrode, the porous inorganic layer being binder-free and having a porosity of 20 to 70% by volume, preferably 25 to 65% by volume, even more preferably 30 to 60% by volume, the manufacturing method being characterized in that:

(a) A first porous electrode layer is deposited on the substrate,

(a1) The first electrode layer is deposited from a first colloidal suspension;

(a2) Drying and consolidating the layer obtained in step (a 1) by pressing and/or heating to obtain a first porous electrode; optionally, a third layer is formed on the substrate

(a3) The porous layer obtained in step (a 2) then receives a coating of electronically conductive material on and within its pores;

it should be understood that:

the first porous electrode layer may be deposited on the first electronic current collector by performing the sequence of steps (a 1) and (a 2) and optionally step (a 3), or

-a first electrode layer may be deposited beforehand on an intermediate substrate in step (a 1), dried, then separated from said intermediate substrate to be consolidated by pressing and/or heating to obtain a first porous electrode plate, then placed on said first electronic current collector, and said first porous electrode may have been subjected to step (a 3);

(b) Depositing a porous inorganic layer of inorganic material E which must be an electrical insulator on said first porous electrode deposited or placed in step (a),

(b1) The porous inorganic layer is deposited by a second colloidal suspension of particles of inorganic material E;

(b2) Drying the layer obtained in step (b 1), preferably under air flow, and heat treatment at a temperature lower than 600 , preferably lower than 500 , to obtain a porous inorganic layer, thereby obtaining the assembly consisting of porous electrode and porous separator;

it should be understood that

-the porous inorganic layer may have been deposited on the first electrode layer by performing the sequence of steps (b 1) and (b 2), or the inorganic layer may be pre-deposited on an intermediate substrate in step (b 1), dried and then separated from the intermediate substrate to be consolidated by pressing and/or heating before or after deposition on the first electrode layer to obtain a porous inorganic layer;

-the first porous electrode layer and the porous inorganic layer are deposited by a technique selected from the group consisting of: electrophoresis, extrusion, printing methods, preferably selected from inkjet printing and flexographic printing, and coating methods, preferably selected from roll coating, curtain coating, doctor blade coating, slot die coating, dip coating;

-the first porous electrode layer and the porous inorganic layer are deposited from a colloidal solution comprising

Aggregate or agglomerate of monodisperse nanoparticles of at least one active material PA or PC or at least one inorganic material E of the first electrode, said nanoparticles having an average primary diameter D ₅₀ From 2nm to 100nm, preferably from 2nm to 60nm, the average diameter D of the aggregates or agglomerates ₅₀ 50nm to 300nm, preferably 100nm to 200nm, or

Non-agglomerated or non-agglomerated primary particles of at least one active material PA or PC or at least one inorganic material E of the first electrode, of primary diameter D ₅₀ 200nm to 10. Mu.m, preferably 300nm to 5. Mu.m,

it is known that:

if the first porous electrode is intended to be used as anode in the cell, the material PA is selected from: nb (Nb) _2- _x M ¹ _x O _5- M ³ Wherein

And wherein 0.ltoreq.x.ltoreq.1 and 0.ltoreq.delta.ltoreq.2,

Nb _18-x M ¹ _x W _16-y M ² _y O _93- M ³ wherein

M ¹ and M ² May be the same as or different from each other,

And wherein x is 0.ltoreq.1, y is 0.ltoreq.2 and delta is 0.ltoreq.2,

Nb _16-x M ¹ _x W _5-y M ² _y O _55- M ³ wherein

M ¹ and M ² May be the same as or different from each other,

And wherein x is 0.ltoreq.1, y is 0.ltoreq.2 and delta is 0.ltoreq.2,

Nb ₂ O _5- wherein delta is more than or equal to 0 and less than or equal to 2, nb ₁₈ W ₁₆ O _93- Wherein delta is more than or equal to 0 and less than or equal to 2, nb ₁₆ W ₅ O _55- Wherein delta is more than or equal to 0 and less than or equal to 2, li is ₄ Ti ₅ O ₁₂ And Li (lithium) ₄ Ti _5-x M _x O ₁₂ Wherein M= V, zr, hf, nb, ta and 0.ltoreq.x.ltoreq.0.25, wherein part of the oxygen atoms may be substituted by halogen atoms and/or may beDoped with halogen atoms;

and if the first porous electrode is intended to be used as a cathode in the battery, the material PC is selected from the group consisting of:

-LiFePO ₄

-LiFeMPO ₄ Wherein M is selected from the group consisting of Mn, ni, co, V,

-oxide LiMn ₂ O ₄ Li _1+x Mn _2-x O ₄ Wherein 0 is<x<0.15LiCoO ₂ LiNiO ₂ LiMn _1.5 Ni _0.5 O ₄ LiMn _1.5 Ni _0.5-x X _x O ₄ Wherein X is selected from Al, fe, cr, co, rh, nd, other rare earth elements such as Sc, Y, lu, la, ce, pr, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, wherein 0<x<0.1LiMn _2-x M _x O ₄ Wherein m= Er, dy, gd, tb, yb, al, Y, ni, co, ti, sn, as, mg or a mixture of these compounds, wherein 0 <x<0.4LiFeO ₂ LiMn _1/3 Ni _1/3 Co _1/3 O ₂ LiNi _0.8 Co _0.15 Al _0.05 O ₂ LiAl _x Mn _2-x O ₄ Wherein 0.ltoreq.x<0.15LiNi _1/x Co _1/y Mn _1/z O ₂ Wherein x+y+z=10;

oxide LiNi _x Co _y Mn _1-x-y O ₂ Wherein 0.ltoreq.x and y.ltoreq.0.5; liNi _x Ce _z Co _y Mn _1-x-y O ₂ Wherein 0.ltoreq.x and y.ltoreq.0.5 and 0.ltoreq.z.

Advantageously, in step (c), a second porous electrode layer is deposited on said porous inorganic layer to obtain a stack comprising the first porous electrode layer, the porous inorganic layer and the second porous electrode layer,

(c1) The second porous electrode layer is deposited from a third colloidal suspension by a technique preferably selected from the group consisting of: electrophoresis, printing methods, preferably selected from inkjet printing and flexographic platesPrinting, and coating method, preferably selected from roll coating, curtain coating, knife coating, slot die coating, dip coating, the third colloidal suspension comprising aggregates or agglomerates of monodisperse primary nanoparticles of at least one active material PA or PC of the second electrode, the primary nanoparticles having an average primary diameter D ₅₀ From 2nm to 100nm, preferably from 2nm to 60nm, the average diameter D of the aggregates or agglomerates ₅₀ 50nm to 300nm, preferably 100nm to 200nm, that is to say the primary diameter D of non-agglomerated or non-aggregated primary particles of the at least one active material PA or PC of the second electrode ₅₀ 200nm to 10. Mu.m, preferably 300nm to 5. Mu.m; and

(c2) Consolidating the layer obtained in step (c 1) by pressing and/or heating to obtain a porous layer; optionally, a third layer is formed on the substrate

(c3) Then receiving a coating of electronically conductive material over and within the pores of the porous layer obtained in step (c 2) to form the second porous electrode;

it is to be understood that the second porous electrode layer may be deposited on the second electronic current collector by performing the sequence of steps (c 1) and (c 2) and, if necessary, (c 3), or the second electrode layer may be previously deposited on an intermediate substrate by performing the sequence of steps (c 1) and (c 2) and, if necessary, (c 3), and then separated from the intermediate substrate to be placed on the porous inorganic layer,

And it should be understood that the second electrode layer is made of material PC in case the first electrode layer has been made of material PA, and the second electrode layer is made of material PA in case the first electrode layer has been made of material PC.

Advantageously, a second component consisting of a second porous electrode and a second porous separator layer is deposited on the first component comprising the first porous electrode and the first porous separator layer, such that said second separator layer is deposited on or placed on said first separator layer to obtain a stack comprising the first porous electrode layer, the porous inorganic layer and the second porous electrode layer.

Advantageously, the average diameter of the pores of the first electrode is less than 50nm and/or the average diameter of the pores of the inorganic layer is less than 50nm and/or the average diameter of the pores of the second electrode is less than 50nm.

Advantageously, the stack comprises a first porous electrode layer, a porous separator and a second porous electrode layer. Advantageously, the stack is impregnated with an electrolyte, preferably a lithium ion carrier phase. Advantageously, the electrolyte, preferably the lithium ion carrier phase, is selected from the group consisting of:

electrolyte consisting of at least one aprotic solvent and at least one lithium salt;

Electrolyte consisting of at least one ionic liquid or polyionic liquid and at least one lithium salt;

a mixture of at least one aprotic solvent and at least one ionic or polyionic liquid and at least one lithium salt;

a polymer having ion conductivity by adding at least one lithium salt; and

a polymer having ion conductivity by adding a liquid electrolyte to the polymer phase or the mesoporous structure,

the polymer is preferably selected from poly (ethylene oxide), poly (propylene oxide), polydimethylsiloxane, polyacrylonitrile, poly (methyl methacrylate), poly (vinyl chloride), poly (vinylidene fluoride), PVDF-hexafluoropropylene.

Advantageously, the material PA is Li ₄ Ti ₅ O ₁₂ And/or the material PC is LiFePO ₄ And/or the material E is Li ₃ PO ₄

Advantageously, the material PA is Li ₄ Ti ₅ O ₁₂ The material PC is LiMn ₂ O ₄ The material E is Li ₃ PO ₄

Advantageously, the material PA is Li ₄ Ti ₅ O ₁₂ The material PC is LiMn _1.5 Ni _0.5 O ₄ The material E is Li ₃ PO ₄

Advantageously, the material PA is Li ₄ Ti ₅ O ₁₂ The material PC is LiNi _1/x Co _1/y Mn _1/z O ₂ Wherein x+y+z=10, and the material E is Li ₃ PO ₄

Advantageously, the thickness of the porous inorganic layer is from 3 m to 20 m, preferably from 5 m to 10 m.

Advantageously, the porous layer of the first electrode has a specific surface area of 10m ² /g to 500m ² /g

Detailed Description

1. Definition of the definition

In the context of this document, the size of a particle is defined by its largest dimension. "nanoparticle" means any particle or object of nanometric dimensions, at least one dimension of which is less than or equal to 100nm.

In the context of this document, the term "electronically conductive oxide" includes electronically conductive oxides and electronically semiconductive oxides.

In the context of this document, an electrically insulating material or layer, preferably an electrically insulating and ion conducting layer, is one having a resistivity (resistance to passage of electrons) of greater than 10 ⁵ Omega cm material or layer. By "ionic liquid" is meant any liquid salt capable of transporting ions, which, unlike all molten salts, has a melting temperature below 100 . Some of these salts remain liquid at room temperature and do not cure even at very low temperatures. Such salts are known as "room temperature ionic liquids", abbreviated as RTILs.

"mesoporous" material refers to any solid having pores in its structure, referred to as "mesopores", which have an intermediate size, i.e. a size of 2nm to 50nm, between the micropore size (width less than 2 nm) and the macropore size (width greater than 50 nm). The term corresponds to the term used by IUPAC (international union of pure and applied chemistry), and is a reference for a person skilled in the art. Thus, the term "nanopore" is not used herein, even though the mesopores defined above have a nano-size in the sense of nanoparticle definition, pores of a size of Yu Jiekong size, which are known to those skilled in the art, are referred to as "micropores".

The concept of porosity (and terms as described above) is presented in article "Texture des materiaux pulverulents or poreux" by rouquerol et al, the corpus "Techniques de l' inganieur", treaty on Analysis and Characterisation, booklet P1050; the article also describes porosity characterization techniques, in particular the BET method.

In the meaning of the present invention, the term "mesoporous layer" refers to a layer having mesopores. As will be explained below, in these layers, mesopores contribute significantly to the total pore volume; this is explained by the expression "mesoporous layer with a mesoporous porosity greater than X% by volume" used in the following description, wherein X% is preferably greater than 25%, preferably greater than 30% and even more preferably between 30% and 50% of the total volume of the layer. The same description applies to pores larger than mesopores, according to the IUPAC definition given above.

The term "aggregate" refers to a weakly bound aggregate of primary particles according to the IUPAC definition. In this case, the primary particles are nanoparticles, the diameter of which can be determined by transmission electron microscopy. The aggregates of aggregated primary nanoparticles can be destroyed (i.e., reduced to primary nanoparticles) typically under the action of ultrasound in a liquid phase suspension, according to techniques known to those skilled in the art.

The term "agglomerates" refers to a strongly bound collection of primary particles or aggregates, according to the IUPAC definition.

Within the meaning of the present invention, the term "electrolyte layer" refers to a layer within an electrochemical device that is capable of functioning according to its intended purpose. For example, in the case where the electrochemical device is a lithium ion secondary battery, the term "electrolyte layer" means a "porous inorganic layer" impregnated with a lithium ion carrier phase. The electrolyte layer is an ionic conductor, but it is electrically insulating.

According to the terminology used by those skilled in the art, the porous inorganic layer in an electrochemical device is also referred to herein as a "separator".

The electrode layers are also porous inorganic layers, but they are referred to herein as "porous electrode layers" or "first porous electrode layers" and "second porous electrode layers" or "porous anode layers" or "porous cathode layers", as appropriate.

Unless otherwise indicated, the size of the particles and agglomerates is D ₅₀ And (3) representing.

2. General description of layers forming a Battery device

According to an essential feature of the method of the invention, the porous electrode layer and the porous inorganic layer (preferably all three-layer mesopores) may be deposited by different methods, in particular by electrophoresis, by extrusion, by coating methods such as dip coating, by roll coating, by curtain coating, by slot die coating or by doctor blade coating, or by printing methods such as inkjet printing or flexography, from suspensions of aggregates or agglomerates of nanoparticles, preferably from concentrated suspensions containing agglomerates of nanoparticles.

Each electrode must be in contact with the surface of a current collector, which must have metallic conductivity. The thickness is advantageously generally from 5 m to 15 m. It is advantageously in the form of a rolled sheet or an electrodeposited sheet (which may be deposited on a polymeric sheet substrate). The current collector may be used as a substrate for depositing the first electrode layer during the fabrication of the battery; it may also be placed on the electrode layer before hot pressing the stack.

The cathode current collector is advantageously selected from the group consisting of: molybdenum, tungsten, tantalum, titanium, chromium, nickel, stainless steel, aluminum, electronically conductive carbon (e.g., graphite, graphene, carbon nanotubes).

The cathode layer should be porous and coated with a material having excellent electron conductivity, preferably metallic conductivity. In a specific embodiment, the cathode layer is mesoporous.

In an advantageous embodiment, which can be combined with all other embodiments described herein, the cathode material is LiFePO ₄ . This material has several advantages. It is stable at high temperatures, insoluble in electrolytes (unlike LiMn ₂ O ₄ Manganese is lost above 55 ). However, this material is an electronic insulator; as described below, it is advantageous to coat the cathode layer with a thin layer of electronically conductive material after it has been deposited. It operates at low potential without oxidation of its metallic current collector Risk; this allows operation at higher temperatures than other cathode materials. For the same reason, more fluid electrolyte formulations, such as dilute ionic liquids, may be used; these liquids oxidize the cathode current collector when the cathode is operated at higher potential, especially at high temperatures. Thus, liFePO is selected ₄ As cathode material, the battery can be operated at higher temperatures for a long time.

The separator must be porous. In certain embodiments, which may be combined with all other embodiments described herein, the separator layer is mesoporous. Its material must remain stable when in contact with the electrode. In an advantageous embodiment, li is used ₃ PO ₄

The anode layer must be porous. In certain embodiments, which may be combined with all other embodiments described herein, the anode layer is mesoporous. The material can be Li ₄ Ti ₅ O ₁₂ . This material has several advantages. And positive LiFePO ₄ In connection, it is possible to design a battery that operates at a steady voltage of around 1.5V, which is compatible with the operating voltages of many electronic circuits. This eliminates the need for an integrated circuit regulator (e.g., an LDO low dropout regulator) or a DC/DC converter to adapt the battery output voltage to the voltage required by the electronic circuit; this is advantageous for microbatteries.

In addition, it is a dimensionally stable material that promotes long life packaging. It also has the advantage of being inexpensive.

Advantageously, the porous anode layer has a coating of a material that is excellent in electron conductivity (preferably metal conductivity); this will be described below. An electron insulator layer having ion conductivity may be deposited on the coating.

The anode current collector is advantageously selected from the group consisting of: molybdenum, tungsten, tantalum, titanium, chromium, copper, stainless steel, aluminum, and electronically conductive carbon. It should be noted that copper is not suitable as an anode current collector when the anode layer is deposited by electrophoresis. Also, titanium is not suitable as a cathode current collector when the cathode layer is deposited by electrophoresis. Since these substrates are cheaper than most of the other substrates mentioned, there are real economic advantages, all other deposition techniques mentioned can be used for the porous electrode layer.

All that has just been described in section 2 applies to porous layers, more specifically to mesoporous layers.

3. Layer deposition and consolidation method

For the manufacture of the layer of the porous electrode or separator, in general, the suspension or paste layer of particles is deposited on the substrate by any suitable technique, in particular by a method selected from the group consisting of: electrophoresis, extrusion, printing methods and preferably inkjet printing or flexographic printing, coating methods and preferably doctor blade coating, roll coating, curtain coating, dip coating or slot die coating. The suspension is usually in the form of an ink, i.e. a rather fluid liquid, but may also have a pasty consistency. The deposition technique and the deposition method must be carried out with a viscosity compatible with the suspension or paste and vice versa.

Generally, in the context of the present invention, the first electrode layer may be deposited on the surface of a substrate capable of functioning as an electronic current collector by performing the sequence of steps (a 1) and (a 2) and, if necessary, step (a 3). Alternatively, the first electrode layer may be previously deposited on the intermediate substrate in step (a 1), dried, and then separated from the intermediate substrate, and consolidated by pressing and/or heating in step (a 2) to obtain the first porous electrode plate, and then placed on the first electronic current collector. The optional step (a 3) may be performed before or after the plate is deposited on the first electronic current collector. During drying and consolidation by extrusion and/or heating, the first electrode layer is subjected to shrinkage, which if the first electrode layer is fixed on a substrate will tend to damage the layer, depending on the thickness of the first electrode layer.

Also, the porous inorganic layer of the inorganic material E may be deposited on the first electrode layer by performing the sequence of steps (b 1) and (b 2), or the inorganic layer of the inorganic material E may be deposited on an intermediate substrate in advance in step (b 1), dried, and then separated from the intermediate substrate, and consolidated by pressing and/or heating before or after being placed on the first electrode layer, to obtain the porous inorganic layer.

These embodiments with an intermediate substrate are particularly suitable for producing layers with a thickness of more than 10 m, more particularly more than 20 m. These thick layers are advantageously used in batteries with capacities greater than 1 mAh.

In general, in the context of the present invention, suspensions or pastes of particles PA, PC or E having a rather broad size range can be used.

According to a first embodiment, which is particularly suitable for manufacturing relatively thin layers (typically not exceeding about 10 m), nanoparticles are used. Their primary size may be about 2nm to about 150nm. These nanoparticles form agglomerates, which are typically 50nm to 300nm in size. Thereby obtaining a mesoporous layer. For example, agglomerates having a size of about 100nm to about 200nm may be used, wherein the primary size of the nanoparticles is about 10nm to about 60nm. The primary particles are advantageously monodisperse in size.

According to a second embodiment, which is particularly suitable for the manufacture of relatively thick layers (typically greater than about 10 m, in particular greater than about 20 m), larger particles are used, the dimensions of which may reach 1 m, or even 5 m, or even 10 m, for layers with a thickness greater than a few tens of m, which may be used for high capacity batteries. In the starting suspension, these particles are generally not agglomerated and their particle size is advantageously monodisperse. This embodiment is particularly suitable when the suspension or paste is deposited on an intermediate substrate.

These thick layers are particularly suitable for the production of batteries, in particular batteries having a capacity of more than 1mAh or a capacity of not more than 1mAh, for example in the form of button cells or SMD components. These thick layers are particularly suitable for single cells, i.e. cells comprising a single cell, called "cell". In these cells, the porous layer of the first electrode (anode and/or cathode) advantageously has a thickness of 4 m to 400 m.

After deposition from the above-mentioned suspension or paste, the deposited layer is then dried. The dried layer is then consolidated to obtain the desired ceramic porous structure. The consolidation will be described below. It comprises a heat treatment and/or a mechanical compression treatment, and possibly a thermo-mechanical treatment, typically a thermo-compression. During such thermal, mechanical or thermo-mechanical treatment, the electrode layer will be free of any organic components and residues (e.g. particle suspension, liquid phase of binder and any surfactant): the electrode layer becomes an inorganic layer (ceramic). Consolidation of the plate is preferably performed after it has been separated from the intermediate substrate, as the latter will degrade during this treatment. In one embodiment, the mechanical compression treatment is performed prior to the heat treatment.

The consolidation conditions, in particular the temperature, duration, pressure applied, depend inter alia on the material, the size of the particles and their crystalline state. During this process, the particles will change shape and form a continuous porous network by interdiffusion (a phenomenon known as "necking"). Their crystalline state will also change, the crystallinity will increase and the number of defects will decrease. Amorphous nanoparticles can crystallize, but this requires relatively high temperatures. The choice of current collector (if any) at this stage must therefore be adapted to the treatment temperature phase.

In particular, it is notable that when the nanopowder deposited on the substrate by inking is amorphous and/or has a number of point defects, it is necessary to carry out a heat treatment which, in addition to consolidation, allows to recrystallize the material to the correct crystalline phase in the correct stoichiometry. For this reason, it is generally necessary to perform the heat treatment in air at a temperature of 500 to 700 . The current collector must be able to withstand this type of heat treatment and it is necessary to use materials that withstand these high temperature treatments, such as stainless steel, titanium, molybdenum, tungsten, tantalum, chromium, and alloys thereof.

When the powders and/or agglomerates of nanoparticles are used in crystalline form, in particular in the case of nanopowders with correct phase and crystal structure obtained by hydro-solvothermal synthesis, then the consolidation heat treatment can be carried out under a controlled atmosphere, which would allow the use of less noble substrates such as nickel, copper, aluminium. Since this synthetic route allows to obtain nanoparticles with very small primary particle sizes, it is also possible to reduce the temperature and/or the duration of the consolidation heat treatment to values close to 350 or 500 , thus enabling to widen the choice of substrates.

However, some synthetic methods known as pseudo-hydrothermal (pseudo-hydrothermal) synthesis produce amorphous nanoparticles that require subsequent recrystallization.

One of the consequences of applying a consolidation heat treatment in air is that no carbon black particles are possible anymore in the electrode to ensure good electron conductivity of the electrode. In fact, during these heat treatments, carbon may be CO ₂ Is calcined (especially when the temperature reaches about 500 c).

The consolidation heat treatment also allows for perfect drying of the electrode layer. Thus, an aqueous and/or organic solvent, such as ethanol, may be used.

Deposition, drying and consolidation of these layers may cause certain problems, which will now be discussed. These problems are in part related to the fact that shrinkage occurs during layer consolidation to create internal stresses.

According to a first embodiment, the electrode layers are each deposited on a substrate capable of functioning as an electronic current collector. The layer comprising the nanoparticle suspension or nanoparticle agglomerate may be deposited on both sides by the deposition techniques described above.

When attempting to increase the thickness of the electrode, shrinkage resulting from consolidation was observed to lead to cracking of the layer or to the generation of shear stress at the interface between the substrate (of fixed dimensions) and the ceramic electrode. When the shear stress exceeds a threshold, the layer may separate from its substrate.

To avoid this, it is preferable to increase the thickness of the electrode by a continuous deposition-sintering operation. The first variant of the first embodiment of the deposited layer gives good results but is not efficient. Alternatively, in a second variant, a layer of greater thickness is deposited on both sides of the perforated substrate. The perforations must have a sufficient diameter so that the two layers of the front and back face contact at the perforations. Thus, during consolidation, the nanoparticles and/or nanoparticle agglomerates of electrode material contacted by the perforations in the substrate are welded together to form attachment points (welds between the deposits on both sides). This limits the loss of adhesion of the layers to the substrate during the consolidation step.

According to the second embodiment, the electrode layer is not deposited on a substrate capable of functioning as an electronic current collector, but is deposited on an intermediate temporary substrate. In particular, a relatively thick layer (referred to as a "green sheet") may be deposited from a more concentrated suspension (i.e., less fluid, preferably pasty) of nanoparticles and/or nanoparticle agglomerates. These thick layers are deposited, for example, by a coating process, preferably by blade coating or by slot die coating. The intermediate substrate may be a polymer sheet, such as poly (ethylene terephthalate), abbreviated as PET or mylar. Upon drying, these layers do not crack. For consolidation by heat treatment (and preferably having been dried), they may be separated from their substrate; after cutting, an electrode plate called a "green" electrode plate is obtained, which after calcination heat treatment and partial sintering will become a porous and self-supporting ceramic plate. This embodiment is particularly suitable for manufacturing relatively thick plates. Without being deposited on a rigid substrate, they can shrink during the consolidation process without risk of cracking.

A three-layer stack is then produced, i.e. two electrode plates having the same polarity are separated by a metal sheet capable of functioning as an electronic current collector. The stack is then assembled by a thermo-mechanical treatment comprising pressing and heat treatment, preferably simultaneously. Alternatively, to promote bonding between the ceramic plate and the metal sheet, the interface may be coated with a layer capable of electronically conductive bonding. The layer may be a sol-gel layer (preferably of a type that allows to obtain the chemical composition of the electrode after heat treatment), possibly loaded with particles of electronically conductive material, which will form a ceramic weld between the porous electrode and the metal sheet. The layer may also consist of a thin layer of unsintered electrode nanoparticles, or a thin layer of conductive binder (e.g. loaded with graphite particles), or a metal layer with a low melting point metal, or a conductive paste.

The sheet metal is preferably a rolled sheet, i.e. obtained by rolling. The rolling may optionally be followed by a final anneal, which may be a softening anneal or a recrystallization (in whole or in part), depending on metallurgical terms. Electrochemical deposition sheets, such as electrodeposited copper sheets or electrodeposited nickel sheets, or graphite sheets, may also be used.

In all cases, a ceramic electrode is obtained which is free of organic binders, is porous, is located on both sides of an electronic current collector, which is typically a current collector with metallic conductivity.

In a variant of the method according to the invention, the current collector with metallic conductivity is not used for the production of the battery. This is possible if the electrode plates have sufficient electron conductivity to ensure that electrons pass through the electrode tips. As described below, if the porous surface is coated with an electron conductive layer, sufficient electron conductivity can be observed.

Note that certain organic binders and/or organic solvents may be used during the layer deposition step. These organic materials are subsequently eliminated by heat treatment in an oxidizing atmosphere; this treatment is pyrolysis.

All that has just been described in section 3 applies to porous layers, more specifically to mesoporous layers.

4. Deposition of thin electron conductor layers in electrode porous networks

This step is optional. The thin electron conductor layer reduces the series resistance of the electrode layer. For electrodes having a thickness of not more than a few micrometers (typically 2 m to 5 m), deposition of such a thin electron conductor layer is not necessary. On the other hand, the deposition of such electronically conductive thin layers represents a preferred embodiment of the invention in order to increase the power of the cell and/or in order to increase the thickness of the electrode (e.g. more than 10 m). For example, in the case of thick individual cells as mentioned in section 3 above, such electronically conductive thin layers are very advantageous, since otherwise their series resistance would be too great.

According to this embodiment of the invention, a coating of electronically conductive material is deposited on and within the pores of the porous electrode layer. Advantageously, at least one of the two porous layers, preferably made of material PC, comprises electricity on and in its poresA coating of sub-conductive material. Such an electronically conductive material may be deposited on a porous layer made of material PC (porous cathode layer) as shown below and/or on a porous layer made of material PA (porous anode layer) as shown below. Such an electron conductive material is advantageously deposited on a porous layer (porous cathode layer) made of material PC as shown below. The coating of electronically conductive material on and within the pores of the porous cathode layer (i.e., the cathode) can prevent parasitic reactions on the cathode surface that can reduce lifetime. The presence of such a coating on a manganese-based cathode can avoid Mn ²⁺ Dissolved in the electrolyte.

Such electronically conductive materials may be deposited by atomic layer deposition techniques (abbreviated ALD) or from liquid precursors. The electronically conductive material may be carbon or an electronically conductive oxide material. The thickness thereof is generally about 0.5nm to 20nm, preferably 0.5nm to 10nm. The coating covers substantially the entire surface of the aperture.

To deposit the carbon layer from the liquid precursor, the mesoporous layer may be immersed in a solution rich in the carbon precursor (e.g., a carbohydrate solution such as sucrose). The layer is then dried and heat treated at a temperature sufficient to pyrolyze the carbon precursor, preferably under an inert atmosphere (e.g., nitrogen). Thus, a very thin carbon coating is formed on the entire inner surface of the porous layer, and the distribution is very uniform. Such a coating gives the electrode good electrical conductivity regardless of the thickness of the coating. Notably, this treatment is possible after sintering because the electrodes are entirely solid, free of organic residues, and resistant to thermal cycling imposed by various heat treatments.

The electronically conductive layer reduces the series resistance of the cell, which is very advantageous for relatively thick electrodes that would otherwise exhibit too high a resistance. This also increases the likelihood of delivering high pulse power with such a battery.

The electron conductive layer also protects the anode surface at high temperatures, preventing possible parasitic reactions between the anode and the electrolyte.

Very advantageously, the electronically conductive material layer is formed by immersion in a liquid phase comprising a precursor of said electronically conductive material, followed by a heat treatment to convert said precursor of electronically conductive material into electronically conductive material. The method is simple, fast, easy to implement, and cheaper than atomic layer deposition technology ALD.

To deposit a layer of electronically conductive oxide material from a liquid precursor, a porous layer (i.e., a porous network of electrodes such as cathodes or anodes) may be immersed in a solution rich in the electronically conductive oxide material precursor. The layer is then dried and subjected to a heat treatment (e.g., calcination, preferably in air or under an oxidizing atmosphere) to convert the electronically conductive oxide material precursor into an electronically conductive oxide material.

Advantageously, the precursor of the electronically conductive oxidizing material is selected from organic salts containing one or more metallic elements capable of forming electronically conductive oxides after a heat treatment (for example calcination, preferably carried out in air or under an oxidizing atmosphere). These metal elements, preferably these metal cations, may advantageously be selected from tin, zinc, indium, gallium or mixtures of two or three or four of these elements. The organic salt is preferably selected from the group consisting of an alkoxide of at least one metal element, an oxalate of at least one metal element, and an acetate of at least one metal element, the alkoxide being capable of forming an electronically conductive oxide upon heat treatment, such as calcination, preferably in air or in an oxidizing atmosphere, the oxalate being capable of forming an electronically conductive oxide upon heat treatment, such as calcination, preferably in air or in an oxidizing atmosphere, the acetate being capable of forming an electronically conductive oxide upon heat treatment, such as calcination, preferably in air or in an oxidizing atmosphere.

Advantageously, the electronically conductive material may be an electronically conductive oxide material, which is preferably selected from the following:

tin oxide (SnO) ₂ ) Zinc oxide (ZnO), indium oxide (In) ₂ O ₃ ) Gallium oxide (Ga) ₂ O ₃ ) Mixtures of two of these oxides correspond, for example, to indium oxide (In ₂ O ₃ ) And tin oxide (Ga) ₂ O ₃ ) Indium tin oxide of the mixture of (a), mixtures of three of these oxidesOr a mixture of four of these oxides,

doped oxides based on zinc oxide, preferably doped with gallium (Ga) and/or aluminum (Al) and/or boron (B) and/or beryllium (Be), and/or chromium (Cr) and/or cerium (Ce) and/or titanium (Ti) and/or indium (In) and/or (Co) and/or nickel (Ni) and/or copper (Cu) and/or manganese (Mn) and/or germanium (Ge),

doped oxides based on indium oxide, preferably doped with tin (Sn) and/or gallium (Ga) and/or chromium (Cr) and/or cerium (Ce) and/or titanium (Ti) and/or indium (In) and/or cobalt (Co) and/or nickel (Ni) and/or copper (Cu) and/or manganese (Mn) and/or germanium (Ge),

-doped tin oxide, preferably doped with arsenic (As) and/or fluorine (F) and/or nitrogen (N) and/or niobium (Nb) and/or phosphorus (P) and/or antimony (Sb) and/or aluminum (Al) and/or titanium (Ti), and/or gallium (Ga) and/or chromium (Cr) and/or cerium (Ce) and/or indium (In) and/or cobalt (Co) and/or nickel (Ni) and/or copper (Cu) and/or manganese (Mn) and/or germanium (Ge).

In order to obtain the electronically conductive material layer, preferably the electronically conductive oxide material layer, from an alkoxide, oxalate or acetate, the porous layer (that is to say the porous network of an electrode, for example a cathode or anode) may be immersed in a solution enriched in the desired electronically conductive material precursor. The electrode is then dried and heat treated at a temperature sufficient to convert (calcine) the target electronically conductive material precursor. Thus, a perfectly distributed coating of electronically conductive material, preferably electronically conductive oxide material, more preferably SnO, is formed over the entire inner surface of the electrode ₂ ZnOIn ₂ O ₃ Ga ₂ O ₃ Or indium tin oxide.

The presence of an electronically conductive coating in the form of an oxide rather than a carbon coating on and within the pores of the porous layer provides the electrode with better electrochemical performance at high temperatures and allows for a significant increase in the stability of the electrode. The fact that an electronically conductive coating in the form of an oxide is used instead of a carbon coating gives, among other things, better electronic conductivity on the final electrode. In fact, the presence of such electronically conductive oxide layers on and in the pores of the porous layer or plate, in particular because the electronically conductive coating is in oxide form, enables an improvement in the final electrode Performance, in particular pressure resistance, temperature resistance, and electrochemical stability of the electrode, in particular when it is in contact with an electrolyte liquid, to reduce the bias resistance of the electrode, even when the electrode is thicker. When the electrode is thick and/or the resistance of the active material of the porous layer is excessively large, an oxide (particularly In ₂ O ₃ SnO ₂ ZnOGa ₂ O ₃ Types or mixtures of one or more of these oxides) are particularly advantageous. The ZnO coating existing on and in the pores of the porous layer enables the electrode to have excellent electrochemical performance at high temperature, and the stability and service life of the electrode are remarkably improved.

The electrode according to the invention is porous, preferably mesoporous, and has a large specific surface area. The increase in specific surface area of the electrode increases the exchange surface by a multiple, thereby increasing the power of the battery, but also accelerating parasitic reactions. These electronically conductive coatings, in the form of oxides on and within the pores of the porous layer, will be able to prevent these parasitic reactions.

Furthermore, due to the very large specific surface area, the effect of these electronically conductive coatings in oxide form on the electronic conductivity of the electrode will be more pronounced than in the case of conventional electrodes with smaller specific surface areas, even though the deposited conductive coating has a smaller thickness. These electronically conductive coatings deposited on and within the pores of the porous layer impart excellent electronic conductivity to the electrode.

Essentially a synergistic combination of a porous layer or plate made of active electrode material and an electronically conductive coating in the form of an oxide disposed on and within the pores of said porous layer or plate, which is capable of improving the final properties of the electrode, in particular to obtain a thick electrode without increasing the internal resistance of the electrode.

Furthermore, electronically conductive coatings in the form of oxides on and within the pores of the porous layer are easier and cheaper to implement than carbon coatings. In fact, unlike the case of carbon coatings, in the case of coatings made of electronically conductive materials in oxide form, the conversion of electronically conductive material precursors to electronically conductive coatings does not need to be carried out under an inert atmosphere.

Optionally, an electrically insulating layer with good ionic conductivity can be deposited on the electronically conductive layer (i.e. on the layer of electronically conductive material coating); the thickness thereof is usually in the range of 1nm to 20 nm. Such an electrically insulating layer having ion conductivity can improve the temperature resistance of the electrode (anode and/or cathode) and ultimately the temperature resistance of the battery.

The ion-conducting and electrically insulating layer may be of inorganic or organic nature. More specifically, in the inorganic layer, for example, an oxide, phosphate or borate that conducts lithium ions may be used, and in the organic layer, a polymer (for example, PEO optionally containing a lithium salt, or a sulfonated tetrafluoroethylene copolymer, such as Nafion, may be used ^TM CAS N31175-20-9)

The layer or group of layers has different functions. The first function is to increase the electron conductivity of the electrode, known as LiMn ₂ O ₄ Or LiFePO ₄ The intrinsic electron conductivity of the electrode is not very high. The second function is to limit ion dissolution from the electrode and migration to the electrolyte, known as LiMn ₂ O ₄ In the electrode, manganese runs the risk of dissolving in certain liquid electrolytes, especially at high temperatures. Finally, thanks to the method used in the present invention, the deposition of said ion-conducting and electrically insulating layer extends to the metallic surface of the current collector and protects the latter from corrosion. If only the electron conductive layer is present, a function of improving the conductivity of the electrode and a function of restricting the dissolution of the electrode will be ensured. If the electron-conducting layer is covered by an ion-conducting layer, the ion-conducting layer will mainly perform a protective function, as described above.

In summary, with these coatings deposited on and within the pores of the porous electrode layer, two roles are sought: increase electron conductivity and prevent dissolution in the electrolyte at high temperatures. Either both effects are obtained by a single coating (i.e. an electronically conductive layer), or a single coating is insufficient to obtain both effects, in which case two layers may be deposited, for example a first layer for obtaining electronic conductivity and a second layer being an ionically conductive and electrically insulating layer; to achieve high temperature protection.

5. Impregnation with liquid electrolyte

This impregnation is explained here for the mesoporous layer. It is also more generally applicable to porous layers having pores larger than mesopores, unless otherwise indicated.

In order for the porous separator layer to be able to perform its electrolyte function, it must be impregnated with a liquid carrying mobile cations; in the case of lithium ion batteries, such cations are lithium cations. Generally, such lithium ion carrier phases are in the group consisting of:

-an electrolyte consisting of at least one aprotic solvent and at least one lithium salt;

-an electrolyte consisting of at least one ionic liquid or polyionic liquid and at least one lithium salt;

-a mixture of at least one aprotic solvent and at least one ionic or polyionic liquid and at least one lithium salt;

-a polymer having ionic conductivity by addition of at least one lithium salt; and

a polymer having ionic conductivity by adding a liquid electrolyte to the polymer phase or to the mesoporous structure,

the polymer is preferably selected from the group consisting of: poly (ethylene oxide), poly (propylene oxide), polydimethylsiloxane, polyacrylonitrile, poly (methyl methacrylate), poly (vinyl chloride), poly (vinylidene fluoride), PVDF-hexafluoropropylene.

The impregnation may be carried out in different steps of the method. This can be done in particular on stacked and hot-pressed cells, that is to say once the cells are completed. Or from the cut edge after encapsulation. More specifically, a stack including a first porous electrode layer, a porous separator, and a second porous electrode layer is impregnated with the liquid electrolyte. The liquid electrolyte immediately enters the pores of the mesoporous layer by capillary action and remains confined in the mesoporous structure. The ionic liquid may be a molten salt at room temperature (these products are known as RTIL, room temperature ionic liquids), or an ionic liquid that is solid at room temperature. Ionic liquids that are solid at room temperature must be heated to liquefy them to impregnate the mesoporous structure; they cure after penetrating the mesoporous structure. In the context of the present invention, RTIL is preferred.

The ion-conducting polymer may be melted, mixed with a lithium salt, and then the molten phase is impregnated into the mesopores. Also, the polymer may be liquid or solid at room temperature and then heated to become liquid so as to impregnate it into the mesoporous structure.

The lithium ion carrier phase may be an electrolyte solution comprising an ionic liquid. The ionic liquid consists of cations and anions in association; the anions and the cations are selected such that the ionic liquid is in a liquid state within the operating temperature range of the accumulator. The ionic liquid has the advantages of high thermal stability, low flammability, non-volatilization, low toxicity and good wettability to ceramics, and can be used as a material of an electrode material.

The cation of the ionic liquid is preferably selected from the group consisting of the following cationic compounds and cationic compound families: imidazolium (for example the cation 1-pentyl-3-methylimidazolium, abbreviated as PMIM), ammonium, pyrrolidinium; and/or the anion of the ionic liquid is preferably selected from the group consisting of the following anionic compounds and families of anionic compounds: bis (trifluoromethanesulfonyl) imide, trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate, 4, 5-dicyano-2- (trifluoromethyl) imidazolium (abbreviated as TDI), bis (oxalic acid) borate (abbreviated as BOB), difluorooxalato borate (abbreviated as DFOB), bis (mandelato) borate (abbreviated as BMB), bis (perfluoropinacol) borate (abbreviated as BPFPB).

In the context of the present invention, ionic liquids give the cell better resistance to high temperatures. When using LiMn-based ₂ O ₄ They are also recommended because under these conditions the dissolution of undesirable manganese is greatly slowed down. Such cathode materials operate at high potentials of about 4.2V, which causes corrosion problems on the collector metal surface; the kinetics of this oxidative corrosion depends on the potential, temperature and the nature of the electrolyte. When using an ionic liquid that is free of solvent, and when the ionic liquid contains no solvent This corrosion can be slowed down when sulfur-containing molecules are present; for this purpose, preference is given to sulfur-free lithium salts in the ionic liquid, such as lithium bis (oxalato) borate (usually abbreviated as "LiBOB", CAS N DEG: 244761-29-3), lithium difluoro (oxalato) borate (usually abbreviated as "LiDFOB", CAS N DEG: 409071-16-5), 4, 5-dicyano-2- (trifluoromethyl) imidazole lithium (usually abbreviated as "LiTDI", CAS N DEG: 761441-54-7). Obviously, this corrosion also depends on the nature of the metal surface, so molybdenum, tungsten and titanium are particularly resistant to corrosion.

On the other hand, for LiFePO ₄ A cathode, a solvent may be used in the formulation of the electrolyte liquid phase because the operating potential of such cathode material is about 3.0V and no corrosion is observed on the metal current collector at this value.

For example, some electrolytes that may be used in the context of the present invention are: comprises N-butyl-N-methyl-pyrrolidinium 4, 5-dicyano-2- (trifluoromethyl) imidazole (Pyr ₁₄ TDI), and an electrolyte comprising 1-methyl-3-propylimidazolium 4, 5-dicyano-2- (trifluoromethyl) imidazole (PMIM-TDI) and 4, 5-dicyano-2- (trifluoromethyl) imidazole lithium (liti). PYR may also be used ₁₄ TFSI and LiTFSI.

Advantageously, the ionic liquid may be of the 1-ethyl-3-methylimidazolium type (also known as EMI ⁺ Or EMIM ⁺ ) And/or n-propyl-n-methylpyrrolidinium (also known as PYR) ₁₃ ⁺ ) And/or n-butyl-n-methylpyrrolidinium (also known as PYR) ₁₄ ⁺ ) Associated with anions of the bis (trifluoromethanesulfonyl) imide (TFSI) and/or bis (fluorosulfonyl) imide (FSI) type. In an advantageous embodiment, the liquid electrolyte contains at least 50 mass% of an ionic liquid, preferably Pyr ₁₄ TFSI

Among other cations useful in these ionic liquids are also PMIM ⁺ . Among other anions useful in these ionic liquids are BF ₄ ^- PF ₆ ^- BOB ^- DFOB ^- BMB ^- BPFPB ^- . In order to form an electrolyte, a lithium salt such as LiTFSI may be dissolved in an ionic liquid used as a solvent, orDissolved in a solvent such as gamma-butyrolactone. Gamma-butyrolactone prevents crystallization of the ionic liquid, resulting in a greater temperature operating range for the latter, especially at low temperatures. Advantageously, when the porous cathode comprises lithiated phosphate, the lithium ion carrier phase comprises a solid electrolyte, such as LiBH ₄ Or LiBH ₄ With one or more compounds selected from LiCl, liI and LiBr. LiBH ₄ Is a good conductor of lithium and has a low melting point, thereby facilitating impregnation into the porous electrode, in particular by impregnation (dipping). LiBH is extremely reducing ₄ Rarely serves as an electrolyte. The use of a protective film on the surface of a porous lithium phosphate electrode prevents the cathode material from being LiBH ₄ Reducing and avoiding degradation thereof.

In general, it is advantageous that the carrier phase of lithium ions comprises 10 to 40 mass% of solvent, preferably 30 to 40 mass% of solvent, even more preferably 30 to 40 mass% of gamma-butyrolactone, glyme or polycarbonate. In an advantageous embodiment, the carrier phase of lithium ions comprises more than 50 mass% of at least one ionic liquid and less than 50% of solvents, which limits the safety and the risk of ignition in case of failure of a battery comprising such a lithium ion carrier phase.

In an advantageous embodiment, the lithium-ion carrier phase comprises:

-a lithium salt or a mixture of lithium salts selected from: liTFSI, liFSI, liBOB, liDFOB, liBMB, liBPFPB and LiTDI; the lithium salt concentration is preferably 0.5mol/L to 4mol/L; applicants have found that the use of an electrolyte with a high concentration of lithium salt can promote very fast charging performance;

-a solvent or solvent mixture having a mass content of less than 40%, preferably less than or equal to 20%; the solvent may be, for example, gamma butyrolactone, polycarbonate, glyme;

Optional additives to stabilize the interface and limit parasitic reactions, such as 4, 5-dicyano-2- (trifluoromethyl) imidazole salt abbreviated as TDI, or ethylene carbonate abbreviated as VC.

In another embodiment, the lithium-ion carrier phase comprises:

-30 to 40% by mass of a solvent, preferably 30 to 40% by mass of gamma-butyrolactone, or PC or glyme, and

-greater than 50% by mass of at least one ionic liquid, preferably greater than 50% by mass of PYR ₁₄ TFSI

For example, the lithium ion carrier phase may be a phase containing PYR ₁₄ The electrolyte solution of TFSI, liTFSI and gamma-butyrolactone preferably contains about 90 mass% PYR ₁₄ TFSI, 0.7M LiTFSI, 2 mass% liti and 10 mass% gamma-butyrolactone.

6. Description of some particularly advantageous batteries

Some particularly advantageous batteries that can be manufactured with the method according to the invention are described herein.

A first advantageous embodiment is a microbattery having:

LiFePO ₄ a cathode having a thickness of about 1 m to about 10 m and a mesoporous porosity of about 35% to about 60%, preferably comprising a coating of an electronically conductive material (a carbon layer having metallic conductivity or a coating of an electronically conductive oxide material), preferably selected from In, on and In its pores ₂ O ₃ SnO ₂ ZnOGa ₂ O ₃ And mixtures of one or more of these oxides), with a thickness of a few nanometers over the entire mesoporous surface;

Li ₃ PO ₄ a separator having a thickness of about 1 m to about 10 m and a mesoporous porosity of about 35% to about 60%;

Li ₄ Ti ₅ O ₁₂ an anode having a thickness of about 1 m to about 10 m and a mesoporous porosity of about 35% to about 60%, preferably comprising a coating of an electronically conductive material (a carbon layer having metallic conductivity or a coating of an electronically conductive oxide material, preferably selected from In ₂ O ₃ SnO ₂ ZnOGa ₂ O ₃ And mixtures of one or more of these oxides), with a thickness of a few nanometers over the entire mesoporous surface;

this layer is not necessary as long as the electronically conductive material coating is not too thick, i.e. as long as the thickness of the electrode is at least kept below about 5 m or 6 m.

The electrolyte may be an ionic liquid, such as EMIM-TFSI+LiFSI or Pyr ₁₄ TFSI+LiTFSI

The operating temperature range of such cells is particularly broad, from about-40 to about +125 . It can be recharged very quickly, reaching 80% of full capacity in less than 3 minutes. It is free of risk of thermal runaway.

A second advantageous embodiment is a microbattery formed from:

LiMn ₂ O ₄ a cathode having a thickness of about 2 m to about 10 m and a mesoporous porosity of about 35% to about 60%, preferably comprising a coating of an electronically conductive material (carbon layer or electronically conductive oxide material coating, preferably selected from In ₂ O ₃ SnO ₂ ZnOGa ₂ O ₃ And mixtures of one or more of these oxides) having a thickness of about 1 nm over the entire mesoporous surface, then covered with a Nafion-type polymer film of about 2 nm;

Li ₄ Ti ₅ O ₁₂ an anode having a thickness of about 2 m to about 10 m and a mesoporous porosity of about 35% to about 60%, preferably comprising a layer of electronically conductive material (carbon layer or electronically conductive oxide material coating, preferably selected from In ₂ O ₃ SnO ₂ ZnOGa ₂ O ₃ And mixtures of one or more of these oxides), the thickness being about 1 to 2 nanometers across the mesoporous surface.

The electrolyte may be an ionic liquid, such as EMIM-TFSI+LiFSI or Pr ₁₄ TSFI+LiTDI or Pyr ₁₄ Tfsi+litfsi. The latter is poorly flowable (and generally requires dilution in a suitable solvent) and stable up to about 5.0V, the former at up to about 4.7V and the latter at up to 4.6V.

Such cells operate at about-40 to about +70 . It can be recharged very quickly, reaching 80% of its full capacity in less than 3 seconds. It is free of risk of thermal runaway.

A third advantageous embodiment is a microbattery having:

LiMn _1.5 Ni _0.5 O ₄ A cathode having a thickness of about 1 m to about 10 m and a mesoporous porosity of about 35% to about 60%, preferably comprising a coating of an electronically conductive material (a carbon layer having metallic conductivity or a coating of an electronically conductive oxide material, preferably selected from In ₂ O ₃ SnO ₂ ZnOGa ₂ O ₃ And mixtures of one or more of these oxides), with a thickness of a few nanometers over the entire mesoporous surface;

The operating temperature range of such cells is particularly broad, from about-40 to about +85 . It can be recharged very quickly, reaching 80% of full capacity in less than 3 minutes. It is free of risk of thermal runaway.

A fourth advantageous embodiment is a microbattery having:

LiNi _1/x Co _1/y Mn _1/z O ₂ a cathode, wherein x+y+z=10, having a thickness of about 1 m to about 10 m, having a mesoporous porosity of about 35% to about 60%, preferably comprising a coating of an electronically conductive material (a carbon layer having metallic conductivity or a coating of an electronically conductive oxide material, preferably selected from In ₂ O ₃ SnO ₂ ZnOGa ₂ O ₃ And mixtures of one or more of these oxides), with a thickness of a few nanometers over the entire mesoporous surface;

Such cells operate at about-20 to about +85 . It has a high capacity. It is free of risk of thermal runaway.

Examples:

example 1:

the battery is made of the following structure:

cathode is made of LiFePO ₄ The metal conductive carbon layer with the thickness of a few nanometers is deposited on the whole mesoporous surface, and the thickness of the metal conductive carbon layer is 7 mu m, and the mesoporous porosity is about 50%. The cathode has a capacity of about 145mAh/g

The diaphragm is made of Li ₃ PO ₄ Made into a thickness of about 6 mum, mesoporous porosity is about 50%.

The anode is made of Li ₄ Ti ₅ O ₁₂ The porous metal film is prepared by depositing a metal conductive carbon layer with the thickness of a few nanometers on the whole mesoporous surface, wherein the thickness of the metal conductive carbon layer is 8 mu m, and the mesoporous porosity is about 50%. The cathode has a capacity of about 130mAh/g

The electrolyte is 0.7M of EMIM-TFSI+LiTFSI ionic liquid or 0.7M of ionic liquid Pyr at all times ₁₄ TFSI+LiTFSI

Such a battery has the following features:

example 2:

the microbattery is made of the following structure:

cathode is made of LiMn ₂ O ₄ The porous ceramic is prepared by depositing a metal conductive carbon layer with the thickness of a few nanometers on the whole mesoporous surface, wherein the metal conductive carbon layer is 8 mu m thick and the aluminum oxide layer with the thickness of a few nanometers is deposited on the carbon layer. The capacity of the cathode was about 130mAh/g.

The diaphragm is made of Li ₃ PO ₄ Made to have a thickness of about 6 m and a mesoporous porosity of about 50%.

The anode is made of Li ₄ Ti ₅ O ₁₂ The porous ceramic material is prepared by the method, the thickness of the porous ceramic material is 8 mu m, the mesoporous porosity is about 50%, the whole mesoporous surface is provided with a metal conductive carbon layer with the thickness of a few nanometers, and an alumina layer with the thickness of a few nanometers is arranged on the carbon layer. The cathode has a capacity of about 130mAh/g

The electrolyte is 0.7M ionic liquid Pyr ₁₄ TFSI+LiTFSI

Such a battery has the following features:

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Claims

1. a lithium ion battery, preferably selected from the group consisting of a microbattery having a capacity of no more than 1mA h and a battery having a capacity of greater than 1mA h, comprising at least one stack comprising, in order: a first electronic current collector, a first porous electrode, a porous separator, a second porous electrode and a second electronic current collector, the electrolyte of the battery being known to be a liquid filled with lithium ions confined in a porous layer, the battery being characterized in that:

the first electrode is an anode comprising a porous layer made of a material PA selected from the group consisting of:

Nb _2-x M ¹ _x O _5- M ³ wherein

And wherein 0.ltoreq.x.ltoreq.1 and 0.ltoreq.delta.ltoreq.2,

Nb _18-x M ¹ _x W _16-y M ² _y O _93- M ³ wherein

M ¹ And M ² May be the same as or different from each other,

And wherein x is 0.ltoreq.1, y is 0.ltoreq.2 and delta is 0.ltoreq.2,

Nb _16-x M ¹ _x W _5-y M ² _y O _55- M ³ wherein

M ¹ And M ² Is at least one element selected from the group consisting of: nb, V, ta, fe, co, ti, bi, sb, as, P, cr, mo (V),W, B, na, mg, ca, ba, pb, al, zr, si, sr, K, ge, ce, cs and Sn;

M ¹ and M ² May be the same as or different from each other,

And wherein x is 0.ltoreq.1, y is 0.ltoreq.2 and delta is 0.ltoreq.2,

Nb ₂ O _5- wherein delta is more than or equal to 0 and less than or equal to 2, nb ₁₈ W ₁₆ O _93- Wherein delta is more than or equal to 0 and less than or equal to 2, nb ₁₆ W ₅ O _55- Wherein delta is more than or equal to 0 and less than or equal to 2, li is ₄ Ti ₅ O ₁₂ And Li (lithium) ₄ Ti _5-x M _x O ₁₂ Wherein m= V, zr, hf, nb, ta and 0.ltoreq.x.ltoreq.0.25, wherein part of the oxygen atoms may be substituted by halogen atoms and/or may be doped by halogen atoms, and the layer is binder-free, has a porosity of 20 to 70% by volume, preferably 25 to 65% by volume, even more preferably 30 to 60% by volume,

-the separator comprises a porous inorganic layer made of an electrically insulating inorganic material E, preferably selected from:

Al ₂ O ₃ SiO ₂ ZrO ₂ a kind of electronic device

Material selected from: lithiated phosphate optionally containing at least one element selected from the group consisting of: al, ca, B, Y, sc, ga, zr; or lithiated borates, which may optionally contain at least one element from the group consisting of: al, ca, Y, sc, ga, zr;

The material is preferably selected from the group consisting of: lithiated phosphates, preferably selected from: naSICON type lithiated phosphate, li ₃ PO ₄ LiPO ₃ Li ₃ Al _0.4 Sc _1.6 (PO ₄ ) ₃ Called "LASP"; li (Li) _1+x Zr _2-x Ca _x (PO ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 0.25; li (Li) ₁₊ _2x Zr _2-x Ca _x (PO ₄ ) ₃ Where 0.ltoreq.x.ltoreq.0.25, e.g. Li _1.2 Zr _1.9 Ca _0.1 (PO ₄ ) ₃ Or Li (lithium) _1.4 Zr _1.8 Ca _0.2 (PO ₄ ) ₃ LiZr ₂ (PO ₄ ) ₃ Li _1+3x Zr ₂ (P _1-x Si _x O ₄ ) ₃ 1.8 of<x<2.3Li _1+6x Zr ₂ (P _1-x B _x O ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 0.25; li (Li) ₃ (Sc _2-x M _x )(PO ₄ ) ₃ Wherein M=Al or Y and 0.ltoreq.x.ltoreq.1; li (Li) _1+x M _x (Sc) _2-x (PO ₄ ) ₃ Wherein M=Al, Y, ga or a mixture of the three elements and 0.ltoreq.x.ltoreq.0.8; li (Li) _1+x M _x (Ga _1-y Sc _y ) _2-x (PO ₄ ) ₃ Wherein 0.ltoreq.x.ltoreq.0.8, 0.ltoreq.y.ltoreq.1 and M=Al and/or Y; li (Li) _1+x M _x (Ga) _2-x (PO ₄ ) ₃ Wherein M=Al and/or Y and 0.ltoreq.x.ltoreq.0.8; li (Li) _1+x Al _x Ti _2-x (PO ₄ ) ₃ Wherein 0.ltoreq.x.ltoreq.1, called "LATP"; or Li (lithium) _1+x Al _x Ge _2-x (PO ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 1 is called as 'LAGP'; or Li (lithium) _1+x+z M _x (Ge _1-y Ti _y ) _2- _x Si _z P _3-z O ₁₂ Wherein 0.ltoreq.x.ltoreq.0.8 and 0.ltoreq.y.ltoreq.1.0 and 0.ltoreq.z.ltoreq.0.6 and M=Al, ga or Y or a mixture of two or three of these elements; li (Li) _3+y (Sc _2-x M _x )Q _y P _3-y O ₁₂ Wherein m=al and/or Y and q=si and/or Se, 0.ltoreq.x.ltoreq.0.8 and 0.ltoreq.y.ltoreq.1; or Li (lithium) _1+x+y M _x Sc _2-x Q _y P _3-y O ₁₂ Wherein m=al, Y, ga or a mixture of these three elements and q=si and/or Se, 0.ltoreq.x.ltoreq.0.8 and 0.ltoreq.y.ltoreq.1; or Li (lithium) _1+x+y+z M _x (Ga _1-y Sc _y ) _2-x Q _z P _3-z O ₁₂ Wherein x is more than or equal to 0 and less than or equal to 0.8, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.6,

wherein m=al and/or Y and q=si and/or Se; or Li (lithium) _1+x Zr _2-x B _x (PO ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 0.25; or Li (lithium) ₁₊ _x M ³ _x M _2-x P ₃ O ₁₂ Wherein 0.ltoreq.x.ltoreq.1 and M ³ Cr, V, ca, B, mg, bi and/or Mo, m= Sc, sn, zr, hf, se or Si, or mixtures of these elements;

The porous inorganic layer is binder-free and has a porosity of 20 to 70% by volume, preferably 25 to 65% by volume, even more preferably 30 to 60% by volume;

the second electrode is a cathode comprising a porous layer made of a material PC selected from the group consisting of:

-LiFePO ₄

-LiFeMPO ₄ Wherein M is selected from the group consisting of Mn, ni, co, V,

-oxide LiMn ₂ O ₄ Li _1+x Mn _2-x O ₄ Wherein 0 is<x<0.15LiCoO ₂ LiNiO ₂ LiMn _1.5 Ni _0.5 O ₄ LiMn _1.5 Ni _0.5-x X _x O ₄ Wherein X is selected from Al, fe, cr, co, rh, nd, other rare earth elements such as Sc, Y, lu, la, ce, pr, pm, sm, eu, gd, tb, dy, ho, er, tm, yb and wherein 0<x<0.1LiMn _2-x M _x O ₄ Wherein m= Er, dy, gd, tb, yb, al, Y, ni, co, ti, sn, as, mg or a mixture of these compounds and wherein 0<x<0.4LiFeO ₂ LiMn _1/3 Ni _1/3 Co _1/3 O ₂ LiNi _0.8 Co _0.15 Al _0.05 O ₂ LiAl _x Mn _2-x O ₄ Wherein 0.ltoreq.x<0.15LiNi _1/x Co _1/y Mn _1/z O ₂ Wherein x+y+z=10;

-Li _1+x Nb _y Me _z A _p O ₂ Wherein a and Me are each at least one transition metal selected from the group consisting of: sc, ti, V, cr, mn, fe, co, ni, cu, zn, Y, zr, nb, mo, tc, ru, rh, pd, ag, cd, hf, ta, W, re, os, ir, pt, au, hg, and 0.6 therein <x<10<y<0.50.25z<1, a step of; wherein A is not equal to Me, A is not equal to Nb, and p is not less than 0 and not more than 0.2;

-Li _x Nb _y-a N _a M _z-b P _b O _2-c F _c 1.2 therein<x1.750y<0.550.1<z<10a<0.50b<.10c<0.8; and wherein M, N and P are each at least one element selected from the group consisting of: ti, ta, V, cr, mn, fe, co, ni, cu, zn, al, zr, Y, mo, ru, rh and Sb;

2. A battery according to claim 1, characterized in that at least one of the two porous layers, preferably a porous layer made of material PC, comprises a coating of an electronically conductive material, preferably carbon or an electronically conductive oxide material, more preferably an electronically conductive oxide material selected from the group consisting of:

Tin oxide (SnO) ₂ ) Zinc oxide (ZnO), indium oxide (In) ₂ O ₃ ) Gallium oxide (Ga) ₂ O ₃ ) Mixtures of two of these oxides correspond, for example, to indium oxide (In ₂ O ₃ ) And tin oxide (Ga) ₂ O ₃ ) Indium tin oxide of the mixture of these oxides, a mixture of three of these oxides or a mixture of four of these oxides,

doped oxides based on zinc oxide, preferably doped with gallium (Ga) and/or aluminum (Al) and/or boron (B) and/or beryllium (Be), and/or chromium (Cr) and/or cerium (Ce) and/or titanium (Ti) and/or indium (In) and/or cobalt (Co) and/or nickel (Ni) and/or copper (Cu) and/or manganese (Mn) and/or germanium (Ge),

3. A battery according to claim 2, characterized in that the electronically conductive material coating is coated with an electrically insulating and ionically conductive layer, preferably having a thickness of 1nm to 20nm.

4. A battery according to any of claims 1 to 3, characterized in that the average diameter of the pores of the first electrode is less than 50nm and/or the average diameter of the pores of the inorganic layer is less than 50nm and/or the average diameter of the pores of the second electrode is less than 50nm.

5. The battery according to any of claims 1 to 4, characterized in that the stack comprising a first porous electrode layer, a porous separator and a second porous electrode layer is impregnated with an electrolyte, preferably a lithium ion carrier phase.

6. The battery of claim 5, wherein the electrolyte is selected from the group consisting of:

a polymer having ion conductivity by adding at least one lithium salt; and

7. The battery according to any one of claims 1 to 6, characterized in thatWhere the material PA is Li ₄ Ti ₅ O ₁₂ And/or the material PC is LiFePO ₄ And/or the material E is Li ₃ PO ₄

8. The battery according to any one of claims 1 to 6, characterized in that the material PA is Li ₄ Ti ₅ O ₁₂ The material PC is LiMn ₂ O ₄ The material E is Li ₃ PO ₄

9. The battery according to any one of claims 1 to 6, characterized in that the material PA is Li ₄ Ti ₅ O ₁₂ The material PC is LiMn _1.5 Ni _0.5 O ₄ The material E is Li ₃ PO ₄

10. The battery according to any one of claims 1 to 6, characterized in that the material PA is Li ₄ Ti ₅ O ₁₂ The material PC is LiNi _1/x Co _1/y Mn _1/z O ₂ Wherein x+y+z=10, and the material E is Li ₃ PO ₄

11. A method of manufacturing a lithium ion battery according to any one of claims 1 to 10, the battery comprising at least one stack comprising, in order: a first electronic current collector, a first porous electrode, a porous separator, a second porous electrode, and a second electronic current collector, the electrolyte of the battery being known to be a lithium ion-filled liquid confined in the porous layer;

The first electrode comprises a porous layer deposited on the substrate, the porous layer being binder-free and having a porosity of 20 to 70% by volume, preferably 25 to 65% by volume, even more preferably 30 to 60% by volume, and the separator comprises a porous inorganic layer deposited on the electrode, the porous inorganic layer being binder-free and having a porosity of 20 to 70% by volume, preferably 25 to 65% by volume, even more preferably 30 to 60% by volume, the manufacturing method being characterized in that:

(a) A first porous electrode layer is deposited on the substrate,

(a1) The first electrode layer is deposited from a first colloidal suspension;

(a2) Drying and consolidating the layer obtained in step (a 1) by pressing and/or heating to obtain a first porous electrode; and optionally

it should be understood that:

-the first electrode layer may be deposited beforehand on an intermediate substrate in step (a 1), dried, then separated from the intermediate substrate, consolidated by pressing and/or heating to obtain a first porous electrode plate, then placed on the first electronic current collector, and the first porous electrode may have been subjected to step (a 3);

(b1) The porous inorganic layer is deposited from a second colloidal suspension of particles of material E;

(b2) Drying the layer obtained in step (b 1), preferably under an air flow, and performing a heat treatment at a temperature lower than 600 , preferably lower than 500 , to obtain a porous inorganic layer, thereby obtaining the assembly consisting of porous electrode and porous separator;

it should be understood that

-a porous inorganic layer may be deposited on the first electrode layer by performing the sequence of steps (b 1) and (b 2), or the inorganic layer may be pre-deposited on an intermediate substrate in step (b 1), dried and then separated from the intermediate substrate, consolidated by pressing and/or heating before or after being placed on the first electrode layer, to obtain a porous inorganic layer;

-the first porous electrode layer and the porous inorganic layer are deposited by a technique selected from the group consisting of: electrophoresis, extrusion, printing methods are preferably selected from inkjet printing and flexographic printing, and coating methods are preferably selected from roll coating, curtain coating, doctor blade coating, slot die coating, dip coating;

Aggregate or agglomerate of monodisperse primary nanoparticles of at least one active material PA or PC or at least one inorganic material E of the first electrode, said primary nanoparticles having an average primary diameter D ₅₀ From 2nm to 100nm, preferably from 2nm to 60nm, the average diameter D of the aggregates or agglomerates ₅₀ 50nm to 300nm, preferably 100nm to 200nm, or

it is known that:

if the first porous electrode is intended to be used as an anode in the battery, the material PA is selected from the group consisting of:

Nb _2-x M ¹ _x O _5- M ³ wherein

And wherein 0.ltoreq.x.ltoreq.1 and 0.ltoreq.delta.ltoreq.2,

Nb _18-x M ¹ _x W _16-y M ² _y O _93- M ³ wherein

M ¹ and M ² May be the same as or different from each other,

And wherein x is 0.ltoreq.1, y is 0.ltoreq.2 and delta is 0.ltoreq.2,

Nb _16-x M ¹ _x W _5-y M ² _y O _55- M ³ wherein

M ¹ and M ² May be the same as or different from each other,

And wherein x is 0.ltoreq.1, y is 0.ltoreq.2 and delta is 0.ltoreq.2,

Nb ₂ O _5- wherein delta is more than or equal to 0 and less than or equal to 2, nb ₁₈ W ₁₆ O _93- Wherein delta is more than or equal to 0 and less than or equal to 2, nb ₁₆ W ₅ O _55- Wherein delta is more than or equal to 0 and less than or equal to 2, li is ₄ Ti ₅ O ₁₂ And Li (lithium) ₄ Ti _5-x M _x O ₁₂ Wherein m= V, zr, hf, nb, ta and 0.ltoreq.x.ltoreq.0.25, wherein part of the oxygen atoms may be substituted with halogen atoms and/or may be doped with halogen atoms;

-LiFePO ₄

-LiFeMPO ₄ Wherein M is selected from the group consisting of Mn, ni, co, V,

-oxide LiMn ₂ O ₄ Li _1+x Mn _2-x O ₄ Wherein 0 is<x<0.15LiCoO ₂ LiNiO ₂ LiMn _1.5 Ni _0.5 O ₄ LiMn _1.5 Ni _0.5-x X _x O ₄ Wherein X is selected from Al, fe, cr, co, rh, nd, other rare earth metals such as Sc, Y, lu, la, ce, pr, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, and wherein 0<x<0.1LiMn _2-x M _x O ₄ Wherein m= Er, dy, gd, tb, yb, al, Y, ni, co, ti, sn, as, mg or a mixture of these compounds, and wherein 0<x<0.4LiFeO ₂ LiMn _1/3 Ni _1/ ₃ Co _1/3 O ₂ LiNi _0.8 Co _0.15 Al _0.05 O ₂ LiAl _x Mn _2-x O ₄ Wherein 0.ltoreq.x<0.15LiNi _1/x Co _1/y Mn _1/z O ₂ Wherein x+y+z=10;

-oxide Li _x M _y O ₂ Wherein 0.6.ltoreq.y.ltoreq.0.85 and 0.ltoreq.x+y.ltoreq.2, and M is selected from Al, ti, cr, mn, fe, co, ni, cu, zn, zr, nb, mo, ru, sn, and Sb or mixtures of these elements; li (Li) _1.20 Nb _0.20 Mn _0.60 O ₂

-Li _x Nb _y-a N _a M _z-b P _b O _2-c F _c 1.2 therein<x1.750y<0.550.1<z<10a<0.50b<.10c<0.8; and wherein M, N and P are each selected from the group consisting ofAt least one element of the group consisting of: ti, ta, V, cr, mn, fe, co, ni, cu, zn, al, zr, Y, mo, ru, rh and Sb;

12. The method of claim 11, wherein in step (c) a second porous electrode layer is deposited on the porous inorganic layer to obtain a stack comprising a first porous electrode layer, a porous inorganic layer and a second porous electrode layer,

(c1) The second porous electrode layer is deposited from a third colloidal suspension by a technique preferably selected from the group consisting of: electrophoresis, extrusion, printing methods, preferably selected from inkjet printing and flexographic printing, and coating methods, preferably selected from roll coating, curtain coating, doctor blade coating, slot die coating, dip coating, said third colloidal suspension comprising: at least one activity of the second electrodeAggregates or agglomerates of monodisperse primary nanoparticles of material PA or PC, the primary nanoparticles having an average primary diameter D ₅₀ From 2nm to 100nm, preferably from 2nm to 60nm, the average diameter D of the aggregates or agglomerates ₅₀ 50nm to 300nm, preferably 100nm to 200nm; or non-agglomerated primary particles of at least one active material PA or PC of the second electrode, of primary diameter D ₅₀ 200nm to 10. Mu.m, preferably 300nm to 5. Mu.m; and

(c2) Consolidating the layer obtained in step (c 1) by pressing and/or heating to obtain a porous layer; and optionally

(c3) The porous layer obtained in step (c 2) then receives a coating of electronically conductive material on and within its pores to form the second porous electrode;

it should be understood that the second porous electrode layer may be deposited on the second electronic current collector by performing the sequence of steps (c 1) and (c 2) and, if necessary, (c 3), or the second electrode layer may have been previously deposited on an intermediate substrate by performing the sequence of steps (c 1) and (c 2) and, if necessary, (c 3), and then have been separated from the intermediate substrate to be placed on the porous inorganic layer,

13. The method of claim 11, wherein a second component consisting of a second porous electrode and a second porous separator layer is deposited on a first component comprising a first porous electrode and a first porous separator layer such that the second separator layer is deposited or placed on the first separator layer to obtain a stack comprising a first porous electrode layer, a porous inorganic layer, and a second porous electrode layer.

14. Method according to any one of claims 11 to 13, characterized in that the deposition of the electronically conductive material coating is performed by atomic layer deposition techniques or by immersion in a liquid phase comprising a precursor of the electronically conductive material, followed by conversion of the precursor into electronically conductive material.

15. The method according to any one of claims 11 to 14, characterized In that the electronically conductive material is carbon or In that the electronically conductive material is selected from In ₂ O ₃ SnO ₂ ZnOGa ₂ O ₃ And mixtures of one or more of these oxides.

16. Method according to claim 15, characterized in that the precursor is a carbon rich compound, such as a carbohydrate, and in that the conversion to electronically conductive material is pyrolysis, preferably under an inert atmosphere.

17. Method according to any one of claims 11 to 16, characterized in that a layer of an electrically insulating body having ion conductivity is deposited on the electronically conductive material coating.

18. The method according to any one of claims 11 or 17, characterized in that the thickness of the porous layer of the first electrode is 4 to 400 m.

19. The method according to any one of claims 11 to 18, characterized in that the thickness of the porous inorganic layer is 3 to 20 m, preferably 5 to 10 m.

20. The method according to any one of claims 11 to 19, characterized in that the porous layer of the first electrode has a specific surface area of 10m ² /g to 500m ² /g

21. The method according to any one of claims 11 to 20, wherein the inorganic material E comprises an electrically insulating material, preferably selected from:

Al ₂ O ₃ SiO ₂ ZrO ₂ a kind of electronic device

the material is preferably selected from the group consisting of: lithiated phosphates, preferably selected from: naSICON type lithiated phosphate, li ₃ PO ₄ LiPO ₃ Li ₃ Al _0.4 Sc _1.6 (PO ₄ ) ₃ Called "LASP"; li (Li) _1+x Zr _2-x Ca _x (PO ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 0.25; li (Li) ₁₊ _2x Zr _2-x Ca _x (PO ₄ ) ₃ Where 0.ltoreq.x.ltoreq.0.25, e.g. Li _1.2 Zr _1.9 Ca _0.1 (PO ₄ ) ₃ Or Li (lithium) _1.4 Zr _1.8 Ca _0.2 (PO ₄ ) ₃ LiZr ₂ (PO ₄ ) ₃ Li _1+3x Zr ₂ (P _1-x Si _x O ₄ ) ₃ 1.8 of<x<2.3Li _1+6x Zr ₂ (P _1-x B _x O ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 0.25; li (Li) ₃ (Sc _2-x M _x )(PO ₄ ) ₃ Wherein M=Al or Y and 0.ltoreq.x.ltoreq.1; li (Li) _1+x M _x (Sc) _2-x (PO ₄ ) ₃ Wherein m=al, Y, ga or a mixture of these three elements, and 0.ltoreq.x.ltoreq.0.8; li (Li) _1+x M _x (Ga _1-y Sc _y ) _2-x (PO ₄ ) ₃ Wherein 0.ltoreq.x.ltoreq.0.8, 0.ltoreq.y.ltoreq.1 and M=Al and/or Y; li (Li) _1+x M _x (Ga) _2-x (PO ₄ ) ₃ Wherein M=Al and/or Y and 0.ltoreq.x.ltoreq.0.8; li (Li) _1+x Al _x Ti _2-x (PO ₄ ) ₃ Wherein 0.ltoreq.x.ltoreq.1, called "LATP"; or Li (lithium) _1+x Al _x Ge _2-x (PO ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 1 is called as 'LAGP'; or Li (lithium) _1+x+z M _x (Ge _1-y Ti _y ) _2- _x Si _z P _3-z O ₁₂ Wherein 0.ltoreq.x.ltoreq.0.8 and 0.ltoreq.y.ltoreq.1.0 and 0.ltoreq.z.ltoreq.0.6 and M=Al, ga or Y or a mixture of two or three of these elements; li (Li) _3+y (Sc _2-x M _x )Q _y P _3-y O ₁₂ Wherein m=al and/or Y and q=si and/or Se, 0.ltoreq.x.ltoreq.0.8 and 0.ltoreq.y.ltoreq.1; or Li (lithium) _1+x+y M _x Sc _2-x Q _y P _3-y O ₁₂ Wherein m=al, Y, ga or a mixture of these three elements and q=si and/or Se, 0.ltoreq.x.ltoreq.0.8 and 0.ltoreq.y.ltoreq.1; or Li (lithium) _1+x+y+z M _x (Ga _1-y Sc _y ) _2-x Q _z P _3-z O ₁₂ Wherein 0.ltoreq.x.ltoreq.0.8, 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.0.6, wherein m=al and/or Y and q=si and/or Se; or Li (lithium) _1+x Zr _2-x B _x (PO ₄ ) ₃ Wherein x is more than or equal to 0 and less than or equal to 0.25; or Li (lithium) ₁₊ _x M ³ _x M _2-x P ₃ O ₁₂ Wherein 0.ltoreq.x.ltoreq.1 and M ³ Cr, V, ca, B, mg, bi and/or Mo, m= Sc, sn, zr, hf, se or Si, or mixtures of these elements.

22. The method of any one of claims 11 to 21, wherein the cathode current collector is made of a material selected from the group consisting of: mo, W, ti, cr, ni, al, stainless steel, electronically conductive carbon and/or anode current collector are made of a material selected from the group consisting of: cu, mo, W, ta, ti, cr stainless steel, electronically conductive carbon.

23. The method according to any one of claims 11 to 22, characterized in that the stack comprising a first porous electrode layer, a porous separator and a second porous electrode layer is impregnated with an electrolyte, preferably a lithium ion carrier phase, selected from the group consisting of:

a polymer having ion conductivity by adding at least one lithium salt; and

24. Use of a battery according to any of claims 1 to 10 at a temperature below-10 and/or above +80.