Method for manufacturing a treated battery holder

Abstract

The present invention relates to a method for manufacturing a treated battery support comprising the following steps: a) depositing on at least a part of the surface of a battery support at least a first layer of an inorganic material; b) depositing on at least a part of the surface of said first layer at least a second layer of a material of formula (I): MFx (I), c) contacting at least one lithium salt of polymer, said polymer comprising at least one hydroxyl group and / or at least one carboxylic acid group, with said second layer to form a third layer situated on the second layer.

Description

Title of the invention: Method for manufacturing a treated battery holder technical field

[0001] The present invention relates to the field of batteries. More particularly, the present invention relates to a method for manufacturing a treated battery support. The invention also relates to said treated battery support. The present invention further relates to a battery cell comprising said treated battery support or the treated battery support obtainable by the manufacturing method according to the invention, a battery comprising said battery cell, and a device comprising said battery. Previous techniques

[0002] An electrochemical cell of an electric battery comprises a positive electrode called the "cathode", a negative electrode called the "anode", an electrolyte allowing the circulation of ions between the anode and the cathode, and anodic and cathodic current collectors carrying, respectively, the anode and the cathode and connecting them to the external circuit.

[0003] The performance of a battery depends on the ionic and electronic transport properties.

[0004] Thermodynamic reactions are initiated during the first charging cycle of the electrochemical cell, and the first ion exchanges between the electrodes take place. Products resulting from these reactions accumulate on the surface of the electrodes to form a layer called the solid-electrolyte interface or SEI layer.

[0005] In batteries, for example lithium-ion batteries, this layer is an essential element for the proper functioning of the electric battery because it conducts lithium ions very well and has the advantage of stopping the catalytic decomposition of the liquid electrolyte solvent.

[0006] The quality of the SEI layer determines the battery life and its formation is therefore an important step.

[0007] The quality of another layer within the battery also affects the battery's lifespan. This is the passivation layer.

[0008] In recent years, artificial passivation layers have been the subject of extensive research. Indeed, it has been discovered that these artificial passivation layers are one of the most promising ways to increase battery life.

[0009] In particular, the passivation layer of an MFX-based material, where M broadly designates a metallic element and x is at least 2, applied by an atomic layer deposition (ALD) process, is a thin and uniform layer that improves the chemical and electrochemical stability of the battery components without significant loss of electrical conductivity. This has, for example, been described in US patent application 2018 / 233770.

[0010] However, this passivation layer is very thin and poorly tolerates the inevitable volume changes during battery charge and discharge cycles. This leads to the appearance of surface defects and undesirable reactions, including chemical and / or electrochemical decomposition, which accumulate at the defect sites, causing a reduction in battery lifespan.

[0011] Other avenues have thus been explored but none of them is totally satisfactory.

[0012] Thus, there is a need to develop a manufacturing process for a treated battery support that avoids chemical and / or electrochemical decomposition reactions, with the aim of improving battery life. Description of the invention

[0013] The invention therefore relates to a method for manufacturing a treated battery holder comprising the following steps:

[0014] a) deposit on at least a part of the surface of a battery support at least a first layer of an inorganic material;

[0015] b) deposit on at least a portion of the surface of said first layer at least a second layer of a material of formula (I): MFX (I),

[0016] in which:

[0017] M represents at least one element selected from the alkaline earth metals, the transition metals, the post-transition metals, and the metalloids, and

[0018] x is an integer at least equal to 2;

[0019] c) to bring into contact at least one lithium salt of polymer, said polymer comprising at least one hydroxyl group and / or at least one carboxylic acid group, with said second layer to form a third layer situated on the second layer.

[0020] The manufacturing process for the treated battery support according to the invention makes it possible to obtain excellent chemical / electrochemical stability on the surface of the third layer. Consequently, the treated battery support obtained is tolerant of volume changes during battery charge and discharge cycles, but also depending on the temperature. Thus, the manufacturing process according to the invention makes it possible to improve the lifespan of the batteries.

[0021] The invention also relates to a treated battery support. Another object of the invention is a battery cell comprising at least one treated battery support according to the invention or capable of being obtained by the manufacturing process of the treated battery support according to the invention, a battery comprising at least one battery cell according to the invention, as well as a device comprising at least one battery according to the invention.

[0022] Other advantages and features of the invention will become more apparent upon examination of the detailed description.

[0023] It is specified that the expression "from... to..." used in this description of the invention should be understood as including each of the limits mentioned.

[0024] As indicated above, the manufacturing process for the treated battery support according to the invention comprises:

[0025] a) deposit on at least a part of the surface of a battery support at least a first layer of an inorganic material.

[0026] Advantageously, the battery support is an anodic current collector, a cathodic current collector, a negative electrode or a positive electrode.

[0027] In a particularly preferred manner, the battery support is a cathode current collector.

[0028] An example of a cathode current collector is an aluminum sheet.

[0029] According to a preferred embodiment, the first layer is deposited over the entire surface of said battery support.

[0030] Advantageously, the inorganic material is chosen from A12O3, Al, AlFyOz, in which 0 < y / z < 2 / 3, aluminium alloys, preferably A12O3.

[0031] Said first layer of an inorganic material can be deposited by any technique known to a person skilled in the art, for example by an atomic layer deposition (ALD) process, or by chemical vapor deposition (CVD).

[0032] The manufacturing process for the treated battery support according to the invention also includes:

[0033] b) deposit on at least a part of the surface of said first layer at least a second layer of a material of formula (I): MFX (I),

[0034] in which:

[0035] M represents at least one element selected from the alkaline earth metals, the transition metals, the post-transition metals, and the metalloids, and

[0036] x is an integer at least equal to 2.

[0037] Advantageously, M is chosen from Al, Mg, Ca, Cu, Cd, Fe, Mn, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi, Ce, Cr, Fe, In, La, Mn, Nd, VO, Y, Ce, Ge, Hf, Si, Sn, Ti, V, Zr, V, Nb, Sb, Ta, Bi, Mo, Re, S and W.

[0038] In a particularly preferred manner, M denotes Al.

[0039] According to a particular embodiment, x goes from 2 to 6.

[0040] In a particularly preferred manner, x is equal to 3.

[0041] According to a preferred embodiment, the material of formula (I): MFX (I) is selected from A1F3, MgF2, CaF2, CuF2, CdF2, FeF2, MnF2, NiF2, PbF2, SnF2, SrF2, XeF2, ZnF2, BF3, BiF3, CeF3, CrF3, FeF3, InF3, LaF3, MnF3, NdF3, VOF3, YF3, CeF4, GeF4, HfF4, SiF4, SnF4, TiF4, VF4, ZrF4, VF5, NbF5, SbF5, TaF5, BiF5, MoF6, ReF6, SF6, WF6 and their composites.

[0042] In a particularly preferred manner, the material of formula (I): MFX (I) is the material A1F3.

[0043] According to a preferred embodiment, the second layer is deposited over the entire surface of said first layer.

[0044] Said second layer in a material of formula (I): MFX (I), can be deposited by any technique known to those skilled in the art, for example by an atomic thin film deposition process or by chemical vapor deposition.

[0045] The manufacturing process for the treated battery support according to the invention also includes:

[0046] c) to bring into contact at least one lithium salt of polymer, said polymer comprising at least one hydroxyl group and / or at least one carboxylic acid group, with said second layer to form a third layer situated on the second layer.

[0047] During this step c), a lithium salt of polymer is brought into contact with the material of the second layer, i.e. the material of formula (I): MFX (I), as defined above.

[0048] The lithium source can be lithium hydroxide.

[0049] Advantageously, the polymer is chosen from polyacrylic acid and polyalcohols, preferably polyacrylic acid.

[0050] A reaction then takes place between the lithium salt of the polymer and the MFX material, resulting in the production of a complexing agent. Specifically, M can then be bonded to a hydroxyl group and / or at least one carboxylic acid group of the polymer to form a complexing agent. In parallel, lithium fluoride (LiF) is also produced.

[0051] Thus, the third layer is made of a material comprising lithium fluoride LiF and at least one compound obtained as a result of the reaction between a lithium salt of polymer and the material of formula (I): MFX (I).

[0052] The compound obtained from said reaction has the advantage of having a chelating effect. The lithium fluoride LiF obtained also has the advantage of being electrochemically stable and insoluble in conventional electrolytes.

[0053] Consequently, a double passivation layer is obtained on the first layer of an inorganic material. This double passivation layer, thanks to the nature of the compounds present, allows for excellent chemical and electrochemical stability on the surface of the third layer.

[0054] Said third layer can be deposited by any technique known to a person skilled in the art, for example by a sol-gel method or by spraying.

[0055] The invention also relates to a treated battery holder comprising:

[0056] - at least a first layer located on at least a part of the surface of said battery support made of an inorganic material;

[0057] - at least a second layer located on at least part of the surface of the first layer, in a material of formula (I): MFX (I),

[0058] in which:

[0059] M represents at least one element selected from the alkaline earth metals, the transition metals, the post-transition metals, and the metalloids, and

[0060] x is an integer at least equal to 2;

[0061] - at least a third layer made of a material comprising lithium fluoride and at least one compound obtained as a result of the reaction between a lithium salt of polymer and the material of formula (I): MFX (I), said polymer comprising at least one hydroxyl group and / or at least one carboxylic acid group.

[0062] Preferably, the various embodiments described above for the manufacturing process of the treated battery support are also valid for the treated battery support, where applicable.

[0063] Another object of the invention is a battery cell comprising at least one treated battery support according to the invention or capable of being obtained by the manufacturing process of the treated battery support according to the invention, preferably obtained by the manufacturing process of the treated battery support according to the invention.

[0064] Another object of the present invention is a battery comprising at least one battery cell as defined above.

[0065] The present invention also relates to a device comprising at least one battery as defined above.

[0066] Said device may be any system incorporating a battery, such as for example an electric or electrified rolling vehicle, in particular a bus, a scooter, a motorcycle, an electronic device, a portable device.

[0067] The present invention is illustrated in a non-limiting manner by the following examples. Examples

[0068] An example of a cathode current collector is an aluminum foil, which is used in the following.

[0069] A first layer of alumina is then deposited on the surface of the aluminum sheet by any technique known to those skilled in the art, in particular by an atomic thin film deposition process.

[0070] Then, a second A1F3 layer is deposited on the surface of the first alumina layer. Said second A1F3 layer is deposited by any technique known to those skilled in the art, in particular by an atomic thin-film deposition process.

[0071] A lithium salt of polyacrylic acid is then brought into contact with said second layer.

[0072] The lithium salt of polyacrylic acid is obtained by a reaction involving lithium hydroxide and polyacrylic acid in aqueous solution. At the end of the reaction, the lithium salt of polyacrylic acid is purified by recrystallization.

[0073] Lithium polyacrylic acid salt, in aqueous solution, is then sprayed onto the surface of the second layer. The water is rapidly removed after spraying by vacuuming, applying heat, or hot pressing.

[0074] Thus, the lithium salt of polyacrylic acid is brought into contact with the second layer in A1F3, and a reaction occurs.

[0075] Lithium fluoride (LiF) and a complexing agent are thus obtained. Indeed, since aluminum can coordinate with multiple oxygen atoms of the lithium salt of polyacrylic acid, it can act as a crosslinking agent. The complexing agent has the advantage of having a chelating effect. Lithium fluoride, for its part, has the advantage of being electrochemically stable and insoluble in conventional electrolytes.

[0076] Consequently, a double passivation layer is obtained on the first alumina layer. This double passivation layer, thanks to the nature of the compounds present, allows for excellent chemical and electrochemical stability on the surface of the third layer, thus making the treated battery support tolerant to volume changes during charge and discharge cycles. batteries. Thus, thanks to this double layer of passivation, the lifespan of the batteries is improved.

Claims

Demands

1. A method for manufacturing a treated battery support comprising the following steps: a) depositing on at least a portion of the surface of a battery support at least one first layer of an inorganic material; b) depositing on at least a portion of the surface of said first layer at least one second layer of a material of formula (I):MFX (I), in which: M represents at least one element selected from the alkaline earth metals, transition metals, post-transition metals, and metalloids, and x is an integer at least equal to 2; c) contacting at least one lithium salt of polymer, said polymer comprising at least one hydroxyl group and / or at least one carboxylic acid group, with said second layer to form a third layer situated on the second layer.

2. Method according to claim 1, characterized in that the battery support is an anodic current collector, a cathodic current collector, a negative electrode or a positive electrode.

3. A method according to claim 1 or 2, characterized in that the inorganic material is selected from A12O3, Al, AlFyOz, in which 0 < y / z < 2 / 3, aluminum alloys, preferably A12O3.

4. Method according to claim 1 or 2, characterized in that M is selected from Al, Mg, Ca, Cu, Cd, Fe, Mn, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi, Ce, Cr, Fe, In, La, Mn, Nd, VO, Y, Ce, Ge, Hf, Si, Sn, Ti, V, Zr, V, Nb, Sb, Ta, Bi, Mo, Re, S and W.

5. A method according to any one of the preceding claims, characterized in that x goes from 2 to 6.

6. A process according to any one of the preceding claims, characterized in that the polymer is selected from polyacrylic acid and polyalcohols, preferably polyacrylic acid.

7. Treated battery support comprising: - at least a first layer located on at least a part of the surface of said battery support in an inorganic material; - at least a second layer located on at least part of the surface of the first layer, of a material of formula (I): MFX (I), in which: M represents at least one element selected from the alkaline earth metals, the transition metals, the post-transition metals, and the metalloids, and x is an integer at least equal to 2; - at least a third layer of a material comprising lithium fluoride and at least one compound obtained as a result of the reaction between a lithium salt of polymer and the material of formula (I): MFX (I), said polymer comprising at least one hydroxyl group and / or at least one carboxylic acid group.

8. Battery cell comprising at least one treated battery holder as defined in the preceding claim or capable of being obtained by the manufacturing process as defined in any one of claims 1 to 6.

9. Battery comprising at least one battery cell as defined in claim 8.

10. Device comprising at least one battery as defined in claim 9.