TERNARY SODIUM MANGANESE BORATE GLASSES, THEIR PROCESS OF OBTAINING THEM, AND THEIR USES AS ACTIVE MATERIALS FOR POSITIVE ELECTRODES

Abstract

The present invention relates to sodium manganese borate ternary glasses and a process for their preparation. The invention also relates to the preparation and use of said glasses as active materials for positive electrodes, particularly metal-ion batteries, as well as said active materials and electrodes per se. (no figure)

Description

Title of the invention: TERNARY SODIUM MANGANESE BORATE GLASSES, THEIR PROCESS FOR OBTAINING THEM, AND THEIR USES AS ACTIVE MATERIALS FOR POSITIVE ELECTRODES

[0001] The present invention relates to sodium manganese borate ternary glasses, as well as a process for their production. The invention also relates to the preparation and use of said glasses as active materials for positive electrodes, in particular for metal-ion batteries, as well as said active materials and electrodes per se.

[0002] LiCoO2 (LCO) is the technology used for the positive electrode of the first lithium-ion battery marketed by Sony in 1991. This technology offers very high energy density and is relatively easy to implement. However, the instability associated with the use of cobalt dioxide (CoO2) makes this technology unreliable from an industrial standpoint, and speculation surrounding cobalt prices increases its cost.

[0003] Among the other well-established positive electrode technologies for Li-ion batteries, LiFePO4 (LFP) is a technology known for its very good power and cycling characteristics, while also having the great advantage of having high intrinsic safety and a very good lifespan, whether calendar or cycling.

[0004] However, the theoretical capacity of LiFePO4 (170 mAh / g) combined with an average operating voltage of 3.2V is an obstacle to its application in batteries requiring high energy densities. This constraint is illustrated by the limited range of electric vehicles (less than 160 km) equipped with such technology, which limits their widespread adoption.

[0005] To increase energy densities, it is generally necessary to develop new cathode materials beyond LFP and LCO that are capable of exchanging more than one Li per transition metal.

[0006] The development of glass-based positive electrodes is an interesting approach, particularly because the glass synthesis process remains easier to implement than other synthesis methods (such as hydrothermal synthesis, for example). It is also easily scalable for large-scale material synthesis. Furthermore, the glassy network forming the structure of glasses is less rigid and consists of a larger fraction of free volume (vacant space) than in their crystalline counterparts. Theoretically, this would therefore allow glasses to easily incorporate and extract alkali ions, and to more readily accept structural changes that may occur during cycling. Due to the numerous accessible oxidation states of vanadium, vanadate-based glass electrodes have been considered as promising alternatives. Currently, in the literature, the best electrochemical performance for a vanadium-based glass is achieved by a material based on the Li2O-B2O3-V2O5 system, reaching 1000 Wh / kg at the active material scale over 10 cycles.

[0007] However, this material remains limited by a fairly low operating potential (2.4 V vs Li+ / Li) and especially by its extremely low first charge (20 mAh / g).

[0008] In addition, vanadium poses toxicity and cost problems which limit its long-term application in the electric mobility sector or stationary storage in particular.

[0009] One objective of the invention is therefore to provide compounds which do not have the aforementioned disadvantages.

[0010] In particular, an objective of the invention is to provide compounds that can be used successfully for the preparation of positive electrodes, in particular metal-ion accumulators (the metal being in particular an alkali or alkaline earth metal, for example Li, Na, K, Mg or Ca), having high capacities and / or high energy densities, in particular higher than those relating to prior art devices, while avoiding economically critical and / or toxic metals, such as cobalt or vanadium.

[0011] Also, the invention relates to a glass of the following formula (I):

[0012] x Na2O - y MnOz- (100-xy) B2O3 (I),

[0013] with:

[0014] 0 < x < 100

[0015] 5 < y < 100

[0016] 5 < x+y <100

[0017] 1 < z < 2.

[0018] By "glass" is meant in particular a metastable, amorphous or substantially amorphous solid compound.

[0019] By "amorphous", we mean in particular a solid compound exhibiting no ordered atomic structure at medium and long distances.

[0020] By "substantially amorphous", it is understood in particular that the compound is more than 97%, in particular more than 98 or 99% amorphous by mass.

[0021] The amorphous character can be determined by any technique well known to those skilled in the art, in particular by ray diffraction (XRD).

[0022] According to a particular embodiment, z is equal to 1.

[0023] According to a particular embodiment, z is equal to 2.

[0024] According to a particular embodiment, z is greater than 1 and less than 2.

[0025] According to a particular embodiment, x is greater than or equal to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13.

[0026] According to a particular embodiment, x is greater than or equal to 1, 5, 10, 15, 20, 25, 30, 40 or 45.

[0027] According to a particular embodiment, y is greater than or equal to 6, 7, 8, 9, 10, 15, 20 or 25.

[0028] According to a particular embodiment, y is greater than or equal to 6, 10, 15, 20, 25, 30, 40 or 45.

[0029] According to a particular embodiment, 6 < x+y < 100, with in particular 8, 10, 15, 20, 25, 30, 35 or 38 < x+y < 100.

[0030] According to a particular embodiment, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 or 90 < x+y < 100.

[0031] According to a particular embodiment, x <95, or even 90, 80, 70, 60, 50 or 45.

[0032] According to a particular embodiment, y <95, or even 90, 80, 70, 60, 50 or 45.

[0033] According to a particular embodiment, x <95, or even 90, 80, 70 or 60, and y <95, or even 90, 80, 70 or 60.

[0034] According to a particular embodiment, x+y < 95, or even 90, 80, 70, 60 or 50, with in particular x+y < 80.

[0035] According to a particular embodiment, 0.25 < x / y < 2, and more particularly 0.25 < x / y < 1, for example approximately 0.5.

[0036] According to a particular embodiment, the invention relates to a glass as defined above, the formula of which is as follows: - 14 Na2O - 29 MnOz- 57 B2O3, in which z is such that defined previously, z being notably equal to 2.

[0037] For any particular formula (I) given, each value of x and y is understood to be within +0.5%, or even +1% or +2% or ±3% or +4% or +5% or +10%. Thus, by way of example, a value of x or y of 60 + 1% includes the values ​​from 59.4 to 60.6.

[0038] According to another aspect, the invention also relates to a method for preparing a glass of formula (I) as defined above, comprising or consisting of a step (i) of quenching a molten mixture (A), which consists of or includes a source of Na2O, a source of MnOz and a source of B2O3, to obtain said glass.

[0039] By "source of Na2O, MnOz or B2O3", we mean in particular any precursor of Na2O, MnOz or B2O3 respectively, that is to say in particular any compound or composition capable of generating Na2O, MnOz or B2O3 respectively, in the conditions described in this text. For example, it could be any composition including Na2O, (Mn, MnO and / or MnO2), or B2O3 respectively.

[0040] All embodiments described above relating to the glass of the invention also apply here, alone or in combination.

[0041] According to a particular embodiment, the hardening can be carried out by casting onto a plate, for example a metallic plate, or accelerated by the application of mechanical stresses, for example by a drop hammer.

[0042] According to a particular embodiment, the process as defined above comprises: - a step (i) of quenching a molten mixture (A), which consists of or comprises a source of Na2O, a source of MnOz and a source of B2O3, to obtain an intermediate glass; - a step (ii) of crushing the intermediate glass obtained at the end of step (i); - a step (iii) of tempering the crushed intermediate glass obtained at the end of step (ii), previously molten, to obtain the glass as defined above.

[0043] According to a particular embodiment, the molten mixture of step (i) as described above is, prior to quenching, at a temperature Tb of 700°C to 1500, for example of about 900°C.

[0044] The temperature Tb is maintained for approximately 1 hour.

[0045] According to a particular embodiment, the molten mixture of step (iii) as described above is, prior to quenching, at a temperature Tb' of 700°C to 1500, for example of about 950°C.

[0046] The temperature Tb' is maintained for example for about 1 hour.

[0047] By "quenching", we mean in particular a change from temperature Tb or Tb' to a lower temperature, in particular ambient temperature, at a rate greater than or equal to about 1000°C / min for a cast quench on plate and greater than or equal to about 10000°C / min for a drop hammer type quench.

[0048] According to a particular embodiment, step (i) as described above is preceded by a step of heating the precursor powder mixture to temperature Ta, followed by a second heating to temperature Tb. The temperature Ta is, for example, approximately 800°C, particularly with a heating rate of approximately 300°C / h.

[0049] The temperature Ta is maintained for approximately 1 hour.

[0050] The temperature rise to the Tbse temperature occurs in particular at a heating rate of approximately 300°C / h. The Tb temperature is, for example, approximately 900°C.

[0051] According to a particular embodiment, the molten mixture of step (iii) as described above is obtained by introducing the crushed intermediate glass of step (ii), as described above, directly at a temperature Tb' of 700°C to 1500, for example of about 950°C.

[0052] According to a particular embodiment, step (i) as described above is preceded by a step of stirring the mixture (A).

[0053] In particular, this agitation is carried out on the mixture (A) before its melting, and optionally on the molten mixture (A), before the quenching step (i).

[0054] According to a particular embodiment, the process according to the invention, as defined above, comprises: - A step (i0) involves heating a precursor mixture (A) consisting of a Na2O source, a MnO2 source, and a B2O3 source. This mixture is brought to temperature Ta and then, using a second heating process, to temperature Tb, in order to obtain a molten mixture (A). The temperature Ta is approximately 800°C, particularly with a heating rate of approximately 300°C / h. The heating to temperature Tb is achieved at a rate of approximately 300°C / h. The temperature Tb is, for example, approximately 900°C. - a step (i) of quenching the molten mixture (A) as obtained in the previous step, to obtain said glass.

[0055] According to a particular embodiment, the process according to the invention, as defined above, comprises: - A step (i0) involves heating a precursor mixture (A) consisting of a Na2O source, a MnO2 source, and a B2O3 source. This mixture is brought to temperature Ta and then, using a second heating process, to temperature Tb to obtain a molten mixture (A). The temperature Ta is, for example, approximately 800°C, particularly with a heating rate of approximately 300°C / h. The heating to temperature Tb is achieved at a rate of approximately 300°C / h. The temperature Tb is, for example, approximately 900°C. - a step (i) of quenching the molten mixture (A) as obtained in the previous step, to obtain an intermediate glass; - a step (ii) of crushing the intermediate glass obtained at the end of step (i); - a step (iii0) of introducing the crushed intermediate glass at a temperature Tb', the temperature Tb' being between 700°C and 1500°C, for example about 900 or 950°C; - a step (iii) of tempering the molten crushed intermediate glass obtained at the end of step (iii0), to obtain the glass as defined previously.

[0056] According to a particular embodiment, the process according to the invention, as defined above, comprises: - A step (i0) of heating, under stirring, a mixture of precursors (A) consisting of a Na2O source, a MnOz source, and a B2O3 source. This mixture is brought to temperature Ta and then, using a second heating process, to temperature Tb, in order to obtain a molten mixture (A). The temperature Ta is, for example, approximately 800°C, particularly with a heating rate of approximately 300°C / h. The heating to temperature Tb is carried out at a rate of approximately 300°C / h. The temperature Tb is, for example, approximately 900°C; - a step (i) of quenching the molten mixture (A) as obtained in the previous step, to obtain said glass.

[0057] According to a particular embodiment, the agitation during step (io) is mechanical agitation, in particular by an agitator blade.

[0058] According to a particular embodiment, the Na2O source comprises or is made up of Na2CO3, NaPO3, Na(OH) and / or NaNO3, in particular Na2CO3.

[0059] According to a particular embodiment, the MnOz source comprises or is made up of MnO and / or MnO2, Mn2O3, Mn(CO3), Mn(SO4), or Mn(OH)2, in particular MnO and / or MnO2.

[0060] When z is equal to 1, in particular, the MnOz source comprises or is made up of MnO2.

[0061] When z is equal to 2, in particular, the MnOz source comprises or is made up of MnO2.

[0062] When z is greater than 1 and less than 2, in particular, the MnOz source comprises or is made up of MnO and MnO2. The proportions of MnO and MnO2 can easily be determined according to the value of z.

[0063] According to a particular embodiment, the B2O3 source comprises or is made up of H3BO3.

[0064] According to another aspect, the invention also relates to a glass that can be obtained according to one of the processes defined above.

[0065] According to another aspect, the invention also relates to a powder made up of or comprising glass particles as defined above.

[0066] According to a particular embodiment, the particles have a size between 0.1 at 100 pm, especially from 0.1 to 50 pm, notably from 1 to 50 pm.

[0067] According to a more particular embodiment, the particles have a size ranging from 0.1 to 5 or even 2 pm.

[0068] All embodiments described above relating to the glass of the invention also apply here, alone or in combination.

[0069] According to a particular embodiment, the powder as defined above is devoid of KBr.

[0070] According to a particular embodiment, the particles have a size ranging from 0.1 to 100 pm, in particular from 50 to 100 pm, or from 0.1 to 50 pm, in particular from 1 to 50 pm.

[0071] According to a more particular embodiment, the particles have a size ranging from 0.1 to 5 or even 2 pm.

[0072] By "size" we mean in particular the largest dimension of a particle.

[0073] This size is in particular an average size determined by laser granulometry.

[0074] According to another aspect, the invention also relates to a powder made of or comprising glass particles as defined above and an electronically conductive additive.

[0075] The electronic conductive additive, well known to those skilled in the art, may consist of or comprise hard carbon and / or graphite, or any other conductive additive.

[0076] According to another aspect, the invention also relates to a powder made up of or comprising glass particles as defined above and an electronically conductive additive, in particular carbon particles.

[0077] All embodiments described above relating to the glass and / or glass particles of the invention also apply here, alone or in combination.

[0078] According to a particular embodiment, the particles have a size ranging from 0.1 to 100 pm, in particular from 0.1 to 50 pm, especially from 1 to 50 pm.

[0079] According to a more particular embodiment, the particles have a size ranging from 0.1 to 5 pm.

[0080] By "carbon particles" we mean particles constituting carbon black.

[0081] By "carbon black" is meant in particular a powdery composition of carbon in amorphous form, which is in particular in the form of a powder consisting of or comprising spherical or spheroid particles of 5 to 500 nm (largest dimension), in particular less than 100 nm.

[0082] According to a particular embodiment, the glass particles are mixed with an electronically conductive additive, in particular carbon particles, thus constituting a composite material. In this composite, the additive particles, in particular carbon particles, are distributed such that they envelop the glass particles.

[0083] According to a particular embodiment, the ratio of the mass of the glass particles to the mass of the electronically conductive additive, in particular carbon particles, is from 90 / 5 or 80 / 10 to 50 / 40, this ratio being for example 70 / 25.

[0084] According to another particular embodiment, the ratio of the mass of the glass particles to the mass of the electronically conductive additive, in particular carbon particles, is from 96 / 2 to 90 / 5.

[0085] According to another aspect, the invention also relates to a powder made up of or comprising glass particles as defined above, an electronically conductive additive, in particular carbon particles, and a binder.

[0086] All embodiments described above relating to the glass and / or glass particles of the invention also apply here, alone or in combination.

[0087] According to a particular embodiment, the binder is a polymer, in particular chosen from polyvinylidene fluoride (PVDF).

[0088] According to a particular embodiment, the powder as defined above comprises, by mass:

[0089] -from 50 to 80% of glass particles as defined above, in particular 70%;

[0090] -from 10 to 40% carbon particles, in particular 25%; and

[0091] -from 5 to 10% binder, in particular 5%.

[0092] According to a particular embodiment, the powder as defined above comprises, by mass:

[0093] -from 90 to 96% of glass particles as defined above;

[0094] -2 to 6% of carbon particles, in particular; and

[0095] -2 to 4% binder.

[0096] According to another aspect, the invention also relates to a method for preparing a powder as defined above, comprising a step a) of grinding a glass as defined above.

[0097] All embodiments described above relating to glass and / or glass particles, and / or a powder of the invention also apply here, alone or in combination.

[0098] According to a particular embodiment, the process of the invention as defined above comprises: a. a first grinding stage, in particular with balls, of a glass as defined above, to obtain a first glass powder; b. a second grinding step, in particular with balls, of a composition comprising the glass powder obtained at the end of the previous grinding, as well as a powder of electronically conductive additive, in particular carbon.

[0099] According to a more particular embodiment, the particles of the first glass powder have a size of 5 or even 10 to 20 pm.

[0100] Grinding according to step a) as described above can be carried out, in particular, using a vibratory mill, especially in dry grinding, or an attrition machine (erosion grinding). In the case of a vibratory mill, the glass is typically placed in a grinding chamber containing one or more grinding media. By means of horizontal oscillations of the grinding chamber, the material is ground by impacts between the grinding media, the chamber, and the material to be ground.

[0101] Ball milling according to a step b) as described above can in particular be carried out using a planetary mill, or a centrifugal mill.

[0102] According to another aspect, the invention also relates to the use of a glass as defined above or of a powder as defined above for the production of an electrode, in particular a positive one, especially for a metal-ion battery.

[0103] All embodiments described above relating to glass and / or glass particles, and / or a powder of the invention also apply here, alone or in combination.

[0104] According to another aspect, the invention also relates to a method for preparing an electrode, in particular a positive one, especially for a metal-ion battery or accumulator, said method comprising a step A) of bringing into contact a powder made up of or comprising glass particles, an electronically conductive additive, in particular carbon particles, and optionally a binder, as defined above, with a conductive support.

[0105] All embodiments described above relating to glass and / or glass particles, and / or a powder of the invention also apply here, alone or in combination.

[0106] According to a particular embodiment, the conductive support is a metallic support, the metal being aluminium (Al) and copper (Cu).

[0107] According to a particular embodiment, the process of the invention as defined above comprises:

[0108] Ao) a step of preparing an ink by adding a solvent, in particular selected from N-methyl-2-pyrrolidone (NMP), or aqueous-based polymers (such as carboxymethylcellulose), to a powder consisting of or comprising glass particles, an electronically conductive additive, in particular carbon particles and optionally a binder, the binder being for example previously dissolved in a solvent, in particular N-methyl-2-pyrrolidone (NMP), as defined above, and, optionally homogenization, in particular by mechanical stirring, to obtain a suspension;

[0109] A) a step A) of bringing into contact a suspension such as obtained at the end of step Ao), with a conductive support, in particular by coating, for example of the "doctor blade" type to obtain a device;

[0110] B) optionally, a drying step for said device;

[0111] C) optionally a shaping step, in particular by pelletizing, of said device, possibly dried, in particular at a temperature of 50 to 100°C, in particular at about 80°C, and / or for 1 to 48 hours, for example for about 24 hours.

[0112] According to another aspect, the invention also relates to a battery or accumulator comprising an electrode, in particular a positive one, comprising a glass as defined above or a powder as defined above.

[0113] All embodiments described above relating to glass and / or glass particles, and / or a powder of the invention also apply here, alone or in combination.

[0114] According to a particular embodiment, the cell or accumulator as defined above further comprises at least one electrolyte, a separator, in particular microporous, and a negative electrode, in particular made of or comprising a metal selected from Li, Na and K.

[0115] These elements are well known to the person skilled in the art, who will be able to select them, in particular from the elements of the trade, according to the needs.

[0116] The negative electrode may also be made of or comprising hard carbon or graphite.

[0117] According to a particular embodiment, the battery or accumulator as defined above has a theoretical specific capacity greater than 80 mAh / g and going for example up to or exceeding about 225.5 mAh / g, or even about 264.7 mAh / g.

[0118] The batteries and accumulators of the invention can, for example, be used in the field of electrical storage, particularly stationary, or in electric mobility, particularly for portable or wearable electronics, in integration into fibers and / or cables, in particular in the context of wired batteries, or for medical use.

[0119] In particular, the batteries and accumulators of the invention can be used in the field of electric mobility, in particular for electric vehicles, plug-in hybrid electric vehicles, hybrid vehicles, or electric 2-wheelers.

[0120] In particular, the batteries and accumulators of the invention can be used in the field of portable power equipment, in particular telephony, laptops, or portable tools.

[0121] According to another aspect, the invention also relates to a battery comprising at least one cell or at least one accumulator as defined above.

[0122] All embodiments described above relating to glass and / or glass particles, and / or a powder of the invention, and / or an electrode, and / or a battery or accumulator also apply here, alone or in combination.

[0123] According to another aspect, the invention also relates to a portable or electric mobility-adapted electrical system, comprising a battery as defined above.

[0124] All embodiments described above relating to glass and / or glass particles, and / or a powder of the invention, and / or an electrode, and / or a battery or accumulator also apply here, alone or in combination. DEFINITIONS

[0125] As understood herein, value ranges in the form of "ab" or "from a to b" or "between a and b" include the bounds a and b, the integers between these bounds, and all other real numbers between these bounds. For example, "1-5", or "from 1 to 5", or "between 1 and 5" denotes the integers 1, 2, 3, 4, and 5, as well as all other real numbers between 1 and 5. Preferred embodiments include each individual integer in the value range, as well as any subcombination of these integers and any set of real numbers between these integers. As an example, preferred values ​​for "1-5" may include the integers 1, 2, 3, 4, 5, 1-2, 1-3, 1-4, 1-5, 2-3, 2-4, 2-5, etc.

[0126] As used in this description, the term "approximately" refers to a range of values ​​within ±10% of a specific value. For example, the expression "approximately 20" includes values ​​within 20 ±10%, that is, values ​​from 18 to 22.

[0127] For the purposes of this description, percentages refer to percentages by mass relative to the total mass of the formulation, unless otherwise specified. FIGURES

[0128] Fig. 1 presents a thermal cycle for the production of 14 Na2O - 57 B2O3 - 29 MnO glass, according to example 1.

[0129] Fig. 2 shows the galvanostatic cycling curves of glass with a composition of 14 Na2O - 57 B2O3 - 29 MnO with a discharge start at C / 100, between 1.5 and 4.5 V, in Li-metal configuration.

[0130] Fig. 3 shows the galvanostatic cycling curves of glass with a composition of 14 Na2O - 57 B2O3 - 29 MnO with a discharge start at C / 100, between 1 and 4.3 V, in Na-metal configuration. EXAMPLES

[0131] Example 1: Preparation of glass 14 Na 2 O - 57 B 2 O 3 - 29 MnO

[0132] The glass in the 14 Na2O - 57 B2O3 - 29 MnO system was produced by air quenching on a metal plate, particularly stainless steel, from a molten bath. Following the first quench ([Fig. 1]), the material is crushed and then hot-reheated in the furnace at 950°C. Intermediate crushing may, if necessary, homogenize the material. The material is held at this temperature for 1 hour before being poured again onto a metal plate.

[0133] The target molar proportion is obtained by weighing the different precursor powders (H3BO3 for B2O3 and MnO for MnO and Na2CO3 for Na2O) constituting the mixture.

[0134] These precursors are then placed in rhodium-plated platinum crucibles to avoid the diffusion of parasitic elements as in the case of alumina crucibles (diffusion of aluminium).

[0135] The melting bath is obtained by subjecting the mixture of precursor powders to a heat treatment ([Fig.l]) allowing the elimination of chemical species from the precursors (CO2, H2O), in particular at 800°C for 2h for the moles of CO2.

[0136] The reaction equation is as follows:

[0137] Na2CO3 + 2(H3BO3) + MnO Na2O + [COJ + [3 H2O] + B2O3 + MnO.

[0138] The raw material (without further heat treatment such as stabilizing annealing) is then analyzed to determine its actual chemical composition, whether it is amorphous or not, as well as its microstructural and elemental homogeneity.

[0139] Initially, analyses by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) as well as measurements by Energy-Dispersive X-ray Spectroscopy (EDX) made it possible to determine the actual composition of the sample.

[0140] The amorphous nature of the material was verified and confirmed by X-ray diffraction on powder.

[0141] Initially, the microstructural homogeneity of the glass was confirmed by Scanning Electron Microscopy (SEM) through the acquisition of backscattered electron images from a polished section of the raw material. By coupling with an Energy-Dispersive X-ray Spectroscopy (EDX) detector, it was possible to obtain scans allowing the quantification of the elements present in the sample, thus confirming the chemical composition.

[0142] Element distribution maps were then obtained, thus allowing verification and confirmation of the homogeneity of the distribution of elements within the sample.

[0143] The glass is then ground for 3 minutes at 30Hz via a vibratory grinder (Retsch MM400) in order to be shaped into a button cell for electrochemical characterization.

[0144] Example 2: Electrochemical Characterizations of the Glasses of the Invention • Electrode preparation#

[0145] Initially, an intimate mixture of active material / carbon black (Super P) in a mass ratio of 70 / 25 was prepared using a high-energy mill (PM 100 planetary mill) in dry mode. The milling protocol lasted a total of 6 hours at 300 rpm, alternating 5 minutes of milling with 5 minutes of rest (to avoid local heating that could lead to potential devitrification / crystallization), resulting in 3 hours of effective milling. The resulting powder was then characterized by X-ray diffraction to ensure that the amorphous nature of the glass / carbon mixture was maintained.

[0146] The resulting glass / carbon powder (i.e., composite material) is then mixed with 5 wt% polymer binder (a 10 wt% solution of polyvinylidene fluoride (PVDF) diluted in N-methyl-2-pyrrolidone (NMP)). A solvent (NMP) is then added to obtain a homogeneous ink of acceptable viscosity for coating. This ink, consisting of a dispersion of composite particles in PVDF and NMP, is mechanically agitated (for 15 minutes at 1000 rotations per minute) using a mechanical disperser (Dispermat). This disperser homogenizes the dispersion and disperses the composite aggregates formed during the grinding step. The ink is then coated using the "doctor blade" method (coating table with slotted squeegee set at 100 pm) onto an aluminum sheet, then dried for 24 hours at 60°C under air to eliminate the residual solvent (NMP).

[0147] After drying, the resulting electrode is cut into 14 mm diameter discs, which are then calendered under a pressure of 10 tonnes. The mass and thickness of the discs were measured. The discs are then vacuum-dried for 48 hours at 80°C to remove residual water. Finally, the electrodes are transferred to a glove box ([H2O] < 1 ppm, [O2] < 1 ppm) for mounting in button cells. • Making button batteries#

[0148] The electrodes are mounted in a so-called half-button cell configuration (CR2032 type format), in a glove box, in a Li-metal, Na-metal, or K-metal configuration. The electrodes are arranged in a lid (a large hood), inside of which an insulating gasket is affixed. Two separators are added to the electrode to be tested: a Viledon felt serving as an electrolyte reservoir, and a Celgard microporous separator preventing sodium dendritic growth. In the case of a K-ion cell, only one separator, the Whatmann separator, was used. A volume of 150 pL of electrolyte is added to the pipette. Then, the counter electrode, a metal foil (Li, Na, or K) deposited on a stainless steel block, is placed over the separators. A spring is placed on the counter electrode, then the half button cell is closed with a small cover (or cap) and crimped.

[0149] Depending on the configuration, the three electrolytes used are as follows: Li-metal: IM of LiPF6 in EC:DMC:EMC (1:1:1 vol.) - Na-metal: IM of NaPF6 in EC:DMC (50% vol.:50% vol.) + 2% mass of FEC - K-metal: 0.7M of KPF6 in EC:DEC (50% vol.:50% vol.) + 2% mass of VC

[0150] With: - EC: ethylene carbonate - DMC: dimethyl carbonate - EMC: ethyl methyl carbonate - DEC: diethyl carbonate - FEC: Ethylene fluorocarbonate - VC: vinylene carbonate • Galvanostatic cycling#

[0151] The performance of the resulting battery is evaluated using an ARBIN type test bench. The batteries are typically cycled at a C / 100 rate, at room temperature, with a potential window between 1.0V and 4.3V or 1.5 and 4.5V. • Examples of galvanic cycling curves#

[0152] The battery is initially placed in a discharge configuration to insert lithium into the glass structure. A galvanostatic cycling test is performed with a discharge start at a terminal potential of 1.5 V vs Li7Li.

[0153] Fig. 2 presents an example of galvanic cycling curves.

[0154] Furthermore, the battery is initially placed in a discharge configuration to introduce sodium into the glass structure. A galvanostatic cycling test is performed with a discharge start using a terminal at a potential of 1.0 V vs Na+ / Na.

[0155] Fig. 3 presents an example of galvanic cycling curves.

Claims

Demands

1. Glass of the following formula (I): x Na2O - y MnOz- (100-xy) B2O3 (I), with: 0 < x < 100 5 < y < 100 5 < x+y < 100 1 < z < 2.

2. Glass according to claim 1, wherein: x+y < 95, or even 90, 80, 70, 60 or 50, the glass being for example the following formula: - 14 Na2O - 29 MnOz- 57 B2O3, in which z is as defined above, z being in particular equal to 2.

3. A method for preparing a glass according to claim 1 or 2, comprising a step (i) of quenching a molten mixture (A), which consists of or comprises a source of Na2O, a source of MnOz and a source of B2O3, to obtain said glass.

4. A process according to claim 3, comprising: - a step (i) of quenching a molten mixture (A), which consists of or comprises a source of Na2O, a source of MnOz and a source of B2O3, to obtain an intermediate glass; - a step (ii) of crushing the intermediate glass obtained at the end of step (i); - a step (iii) of quenching the crushed intermediate glass obtained at the end of step (ii), previously molten, to obtain the glass according to claim 1 or 2; or wherein step (i) as described in claim 3 is preceded by a step of stirring the mixture (A).

5. A method according to any one of claims 3 to 4, wherein: - the Na2O source comprises or is made up of Na2CO3, NaPO3, Na(OH) and / or NaNO3, in particular Na2CO3; - the source of MnOz comprises or is made up of MnO and / or MnO2, Mn2O3, Mn(CO3), Mn(SO4), or Mn(OH)2, in particular MnO and / or MnO2; - the source of B2O3 comprises or is made up of H3BO3.

6. Powder made up of or comprising glass particles as defined in any one of claims 1 to 2, wherein the particles have in particular a size of 0.1 to 100 pm, in particular 0.1 to 50 pm.

7. Powder according to claim 6, further comprising an electronically conductive additive, in particular carbon particles, and optionally, a binder.

8. Electrode, in particular positive, in particular for a metal-ion battery or accumulator, comprising a glass according to claim 1 or 2 or a powder according to claim 6 or 7.

9. A method for preparing an electrode, in particular a positive one, especially for a metal-ion battery or accumulator, said method comprising a step A) of contacting a powder made up of or comprising glass particles, an electronically conductive additive, in particular carbon particles, and optionally a binder, according to any one of claims 6 to 7, with a conductive support.

10. Battery or accumulator comprising an electrode, in particular a positive electrode, comprising a glass according to claim 1 or 2 or a powder according to claim 6 or 7, having in particular a theoretical capacity greater than 80 mAh / g.

11. Battery comprising at least one cell or at least one accumulator according to claim 10.

12. A portable or electrically adapted system for electric mobility, comprising a battery according to claim 11.

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