FR3129936A1 - Process for obtaining a high-entropy oxide - Google Patents

Process for obtaining a high-entropy oxide Download PDF

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Publication number
FR3129936A1
FR3129936A1 FR2112930A FR2112930A FR3129936A1 FR 3129936 A1 FR3129936 A1 FR 3129936A1 FR 2112930 A FR2112930 A FR 2112930A FR 2112930 A FR2112930 A FR 2112930A FR 3129936 A1 FR3129936 A1 FR 3129936A1
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alkali metal
rechargeable battery
entropy oxide
solid
cathode
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FR2112930A
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FR3129936B1 (en
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Arun Kumar MEENA
Sylvain Franger
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Greenfish France
Universite Paris Saclay
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Greenfish France
Universite Paris Saclay
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Priority to FR2112930A priority Critical patent/FR3129936B1/en
Priority to PCT/FR2022/052229 priority patent/WO2023099855A1/en
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Abstract

La présente invention concerne le procédé d’obtention d’un oxyde à haute entropie, un oxyde à haute entropie obtenu selon ce procédé et ayant une conductivité essentiellement de nature ionique, ainsi que l’utilisation de cet oxyde à haute entropie comme électrolyte solide conducteur des ions d’un métal alcalin. La présente invention concerne également le domaine des batteries rechargeables tout solide inorganiques.The present invention relates to the process for obtaining a high entropy oxide, a high entropy oxide obtained according to this process and having an essentially ionic conductivity, as well as the use of this high entropy oxide as a conductive solid electrolyte. alkali metal ions. The present invention also relates to the field of all-solid-state inorganic rechargeable batteries.

Description

Procédé d’obtention d’un oxyde à haute entropieProcess for obtaining a high-entropy oxide

DOMAINE TECHNIQUE DE L’INVENTIONTECHNICAL FIELD OF THE INVENTION

La présente invention concerne le procédé d’obtention d’un oxyde à haute entropie, un oxyde à haute entropie obtenu selon ce procédé et ayant une conductivité essentiellement de nature ionique, ainsi que l’utilisation de cet oxyde à haute entropie comme électrolyte solide conducteur des ions d’un métal alcalin.The present invention relates to the process for obtaining a high entropy oxide, a high entropy oxide obtained according to this process and having an essentially ionic conductivity, as well as the use of this high entropy oxide as a conductive solid electrolyte. alkali metal ions.

La présente invention concerne également le domaine des batteries rechargeables tout solide inorganiques incorporant un tel électrolyte, ainsi que les véhicules, les appareils électroniques autonomes ainsi que les réseaux intelligents d’électricité comportant de telles batteries.The present invention also relates to the field of inorganic all-solid rechargeable batteries incorporating such an electrolyte, as well as vehicles, autonomous electronic devices as well as intelligent electricity networks comprising such batteries.

ETAT DE LA TECHNIQUESTATE OF THE ART

Les batteries actuelles de type Li-ion arrivent au maximum de leurs capacités de stockage d’énergie de l’ordre de 300 Wh/kg. De plus, elles utilisent des matériaux onéreux et/ou dont l’extraction minière pose des problèmes environnementaux, en particulier le cobalt. Elles utilisent un électrolyte liquide, source de vieillissement prématuré et d’insécurité car il peut être à l’origine de fuites ou d’inflammation. L’utilisation d’un électrolyte liquide complique également le recyclage des systèmes en fin de vie du fait de la présence de composés toxiques, difficiles à séparer et à éliminer.Current Li-ion type batteries reach the maximum of their energy storage capacities of around 300 Wh/kg. In addition, they use materials that are expensive and/or whose mining poses environmental problems, in particular cobalt. They use a liquid electrolyte, a source of premature aging and insecurity because it can cause leaks or inflammation. The use of a liquid electrolyte also complicates the recycling of end-of-life systems due to the presence of toxic compounds, which are difficult to separate and eliminate.

Pour la mobilité électrique des voitures ou des avions par exemple, de nouvelles batteries sont nécessaires. Elles doivent être plus performantes avec une densité d’énergie supérieure à 500 Wh/kg, plus sûres car non susceptibles d’emballement thermique ou de s’enflammer et plus respectueuses de l’environnement en utilisant des matériaux moins toxiques, avec moins d’empreinte environnementale et plus facilement recyclables.For the electric mobility of cars or planes, for example, new batteries are needed. They must be more efficient with an energy density greater than 500 Wh/kg, safer because they are not susceptible to thermal runaway or igniting, and more environmentally friendly by using less toxic materials, with less environmental footprint and more easily recyclable.

Les batteries solides constituent une solution à ces problèmes : en effet, elles n’utilisent pas de substances explosives et/ou de substances volatiles, elles ne sont pas sujettes à des phénomènes de fuite, leur fabrication est plus simple et ne nécessite pas d’emballage métallique complexe, elles offrent par ailleurs davantage de flexibilité dans les processus de fabrication et peuvent prendre des formes diverses.Solid-state batteries are a solution to these problems: in fact, they do not use explosive substances and/or volatile substances, they are not subject to leakage phenomena, their manufacture is simpler and does not require complex metal packaging, they also offer more flexibility in manufacturing processes and can take various forms.

Les électrolytes solides usuels sont souvent des sulfures ou des matériaux sulfochlorés qui présentent des problèmes de stabilité. Les électrolytes soufrés vont en effet avoir tendance à se décomposer en présence d’humidité. Les électrolytes solides de type LLZO (Lithium Lanthanum Zirconium Oxide) sont eux très sensibles à l’air et peuvent se carbonater facilement.The usual solid electrolytes are often sulphides or sulphochlorinated materials which present stability problems. Sulfur electrolytes will indeed tend to decompose in the presence of humidity. Solid electrolytes of the LLZO (Lithium Lanthanum Zirconium Oxide) type are very sensitive to air and can carbonate easily.

Par ailleurs, la mauvaise compatibilité de ces électrolytes avec les matériaux usuels d’électrode rend nécessaire :Furthermore, the poor compatibility of these electrolytes with the usual electrode materials makes it necessary:

  • l’inclusion d’un électrolyte polymère dans la cathode jouant à la fois le rôle de conducteur ionique et de liantthe inclusion of a polymer electrolyte in the cathode playing both the role of ion conductor and binder
  • ainsi que l’inclusion de couches additionnelles aux interfaces électrolyte/électrode,as well as the inclusion of additional layers at the electrolyte/electrode interfaces,

Zhou et al (1) décrit une batterie au Na tout solide rechargeable comprenant :
- une anode constituée de Na métal
- une cathode comprenant comme matériau d’insertion le composé NaTi2(PO4)3, du noir de carbone et un électrolyte polymère (poly(ethylene glycol) methyl ether acrylate – CPMEA)
- du NASICON (Na3Zr2Si2PO12) comme électrolyte.Zhou et al (1) describes a rechargeable all-solid Na battery comprising:
- an anode made of Na metal
- a cathode comprising as insertion material the compound NaTi 2 (PO 4 ) 3 , carbon black and a polymer electrolyte (poly(ethylene glycol) methyl ether acrylate – CPMEA)
- NASICON (Na 3 Zr 2 Si 2 PO 12 ) as electrolyte.

Afin d’éviter la croissance de dendrites métalliques, une couche interfaciale est formée in situ en chauffant anode et électrolyte ou bien une couche de polymère de type CPMEA est déposée entre l’anode et l’électrolyte.In order to avoid the growth of metallic dendrites, an interfacial layer is formed in situ by heating anode and electrolyte or else a layer of polymer of the CPMEA type is deposited between the anode and the electrolyte.

La batterie décrite fonctionne à une température de 65°C.The described battery operates at a temperature of 65°C.

Gao et al (2) décrit une batterie au Na tout solide rechargeable comprenant :
- une anode constituée de Na métal
- une cathode comprenant comme matériau d’insertion le composé Na2MnFe(CN)6, du noir de carbone et un électrolyte polymère (oxyde de polyethylène contenant du NaClO4)
- du NASICON (Na3Zr2Si2PO12) comme électrolyte.Gao et al (2) describes a rechargeable all-solid Na battery comprising:
- an anode made of Na metal
- a cathode comprising as insertion material the compound Na 2 MnFe(CN) 6 , carbon black and a polymer electrolyte (polyethylene oxide containing NaClO 4 )
- NASICON (Na 3 Zr 2 Si 2 PO 12 ) as electrolyte.

A l’inverse de Zhou, de façon étonnante, Gao ne décrit pas la formation de dendrites de Na à l’interface sodium/NASICON.Unlike Zhou, surprisingly, Gao does not describe the formation of Na dendrites at the sodium/NASICON interface.

La batterie décrite fonctionne à une température de 65°C.The battery described operates at a temperature of 65°C.

Il est connu (table 1 dans Lu et al (3) et p2184 in Zhou et al (4)) que l’interface entre un électrolyte de type NASICON et une électrode est de faible qualité conduisant à l’existence d’une impédance interfaciale importante. La forte impédance existant entre les grains de l’électrolyte, couplée à cette forte impédance interfaciale, empêche l’utilisation de cet électrolyte à température ambiante.It is known (table 1 in Lu et al (3) and p2184 in Zhou et al (4)) that the interface between a NASICON type electrolyte and an electrode is of low quality leading to the existence of an interfacial impedance important. The high impedance existing between the grains of the electrolyte, coupled with this high interfacial impedance, prevents the use of this electrolyte at room temperature.

L’ajout de composants additionnels ainsi que la mise en œuvre d’étapes supplémentaires de fabrication ne sont pas souhaités industriellement.The addition of additional components as well as the implementation of additional manufacturing steps are not desired industrially.

Il est également préférable que la batterie tout solide fonctionne à température ambiante.It is also preferable that the all-solid-state battery operates at room temperature.

D’un point de vue industriel, reste donc le besoin de développer des batteries tout solide inorganiques, pouvant fonctionner à température ambiante, et incorporant des électrolytes :
- ayant une bonne stabilité facilitant ainsi leur mise en œuvre ;
- et présentant une bonne compatibilité avec les matériaux d’électrode afin :
o de ne pas nécessiter l’utilisation d’un électrolyte polymère dans la cathode comme composant additionnel
o de ne pas nécessiter l’inclusion de couches additionnelles aux interfaces électrolyte/électrodes.From an industrial point of view, there remains the need to develop all-solid inorganic batteries, which can operate at room temperature, and incorporate electrolytes:
- having a good stability thus facilitating their implementation;
- and having good compatibility with electrode materials in order to:
o not to require the use of a polymer electrolyte in the cathode as an additional component
o not requiring the inclusion of additional layers at the electrolyte/electrode interfaces.

Les électrolytes utilisés dans les batteries selon l’invention doivent avoir une conductivité essentiellement ionique pour pouvoir être utilisés en tant qu’électrolyte dans une batterie.The electrolytes used in the batteries according to the invention must have an essentially ionic conductivity in order to be able to be used as electrolyte in a battery.

L’invention propose de nouvelles batteries inorganiques solides, répondant à ce besoin, comprenant une anode à base de métal alcalin et un électrolyte solide de type oxyde à haute entropie.The invention proposes new solid inorganic batteries, meeting this need, comprising an anode based on an alkali metal and a solid electrolyte of the high entropy oxide type.

L’utilisation d’un métal alcalin de type lithium ou sodium en tant qu’anode dans une batterie rechargeable permet d’accroître notablement sa densité d’énergie massique et volumique, grâce, d’une part, aux capacités spécifiques importantes des métaux alcalins (3.861 mAh/g pour Li et 1.166 mAh/g pour Na) comparées au graphite (372 mAh/g) actuellement utilisé dans les batteries Li-ion et grâce, d’autre part, à la compacité unitaire des métaux plus élevée comparée aux électrodes de graphite de compacité proche de 0,3 et donc peu denses.The use of an alkali metal of the lithium or sodium type as anode in a rechargeable battery makes it possible to notably increase its mass and volume energy density, thanks, on the one hand, to the significant specific capacities of the alkali metals (3,861 mAh/g for Li and 1,166 mAh/g for Na) compared to graphite (372 mAh/g) currently used in Li-ion batteries and thanks, on the other hand, to the higher unit compactness of metals compared to graphite electrodes with a compactness close to 0.3 and therefore not very dense.

Les oxydes à haute entropie sont une nouvelle classe de matériaux découverts en 2015 (Rost et al. (5)).High-entropy oxides are a new class of materials discovered in 2015 (Rost et al. (5)).

Un oxyde à haute entropie présente un désordre de configuration, c’est-à-dire qu’il possède une haute entropie, avec une occupation aléatoire des cations métalliques sur le sous-réseau cubique à faces centrées d’une structure cubique de type NaCl tandis que l’autre sous-réseau est occupé par les anions d’oxygène.A high-entropy oxide exhibits configuration disorder, i.e. it possesses high entropy, with random occupation of metal cations on the face-centered cubic sublattice of a NaCl-like cubic structure while the other sublattice is occupied by oxygen anions.

La formule générale d’un oxyde à haute entropie est (MgaCobNicCudZne)O où a, b, c, d et e désignent respectivement la fraction molaire du Mg, du Co, du Ni, du Cu et du Zn par rapport à l’ensemble des éléments métalliques, avec a+b+c+d+e=1. Les éléments métalliques sont présents sous forme de cations divalents.The general formula of a high entropy oxide is (Mg a Co b Ni c Cu d Zn e )O where a, b, c, d and e denote respectively the molar fraction of Mg, Co, Ni, Cu and Zn with respect to all metallic elements, with a+b+c+d+e=1. The metallic elements are present as divalent cations.

Les éléments métalliques de l’oxyde peuvent être au nombre de 5 comme dans la composition générale donnée ci-dessus.The metallic elements of the oxide can be 5 in number as in the general composition given above.

Les éléments métalliques sont présents préférentiellement en quantité équimolaires dans l’oxyde, c’est-à-dire que la fraction molaire de chaque élément métallique est égale à 0,2 (a=b=c=d=e=0,2).The metallic elements are preferably present in equimolar quantities in the oxide, i.e. the molar fraction of each metallic element is equal to 0.2 (a=b=c=d=e=0.2) .

La possibilité d’une substitution de cations métalliques par des ions alcalins a été démontrée (6). Les propriétés de conductivité ionique de tels composés sont connues mais aucune information relative à la stabilité de ces composés ou à leur compatibilité vis-à-vis des matériaux d’électrode n’est divulguée.The possibility of substitution of metal cations by alkaline ions has been demonstrated (6). The ionic conductivity properties of such compounds are known but no information relating to the stability of these compounds or their compatibility with electrode materials is disclosed.

L’invention a pour objet un procédé de préparation d’un oxyde à haute entropie de formule (I) :The subject of the invention is a process for the preparation of a high-entropy oxide of formula (I):

  • AxM1-xO (I) où :
    • A désigne un métal alcalin ;
    • M est une combinaison d’éléments métalliques comprenant au moins 4 éléments choisis parmi le Mg, le Co, le Ni, le Cu et le Zn ;
    • x est la fraction molaire en métal alcalin A par rapport à la combinaison d’éléments métalliques M et au métal alcalin A, et est comprise entre 0,15 et 0,35, de préférence entre 0,30 et 0,35 ;
    • et O désigne l’oxygène ;
    A x M 1-x O (I) where:
    • A denotes an alkali metal;
    • M is a combination of metallic elements comprising at least 4 elements chosen from Mg, Co, Ni, Cu and Zn;
    • x is the molar fraction of alkali metal A relative to the combination of metallic elements M and to the alkali metal A, and is between 0.15 and 0.35, preferably between 0.30 and 0.35;
    • and O denotes oxygen;
  • comprenant les étapes successives suivantes, à partir d’un mélange broyé et compacté d’oxydes binaires des éléments métalliques de M et de carbonate alcalin source de A :
    • chauffage du mélange compacté à une température supérieure à 900°C sous air, puis ;
    • trempe sous pression partielle d’oxygène Poxtelle que 0 Pa ≤ Pox< 2*104Pa du mélange compacté issu de l’étape de chauffe.
    comprising the following successive steps, starting from a crushed and compacted mixture of binary oxides of the metallic elements of M and of alkali carbonate source of A:
    • heating the compacted mixture to a temperature above 900° C. in air, then;
    • quenching under partial oxygen pressure P ox such that 0 Pa≤P ox <2*10 4 Pa of the compacted mixture resulting from the heating step.

L’invention a également pour objet un oxyde à haute entropie tel que défini ci-dessus ayant une conductivité essentiellement de nature ionique.A subject of the invention is also a high-entropy oxide as defined above having a conductivity essentially of an ionic nature.

Préférentiellement, l’élément M est une combinaison des 5 éléments métalliques suivants : le Mg, le Co, le Ni, le Cu et le Zn.Preferably, the element M is a combination of the following 5 metallic elements: Mg, Co, Ni, Cu and Zn.

Préférentiellement, l’oxyde à haute entropie est choisi parmiPreferably, the high-entropy oxide is chosen from

Na0.3(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)0.7O,Li0.3(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)0.7O,Na 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O , Li 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,

Na0.35(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)0.65O et Li0.35(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)0.65O.Na 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O and Li 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O.

Préférentiellement, l’élément M est une combinaison de 4 éléments métalliques choisis parmi le Mg, le Co, le Ni, le Cu et le Zn.Preferably, the element M is a combination of 4 metallic elements chosen from Mg, Co, Ni, Cu and Zn.

Préférentiellement, l’oxyde à haute entropie est choisi parmi
Na0,3(Mg0.2Co0.2Ni0.2Zn0.4)0,7O,
Li0,3(Mg0.2Co0.2Ni0.2Zn0.4)0,7O,
Na0,35(Mg0.2Co0.2Ni0.2Zn0.4)0,65O,
Li0,35(Mg0.2Co0.2Ni0.2Zn0.4)0,65O,
Na0,3(Mg0.2Co0.2Ni0.4Zn0.2)0,7O,
Li0,3(Mg0.2Co0.2Ni0.4Zn0.2)0,7O,
Na0,35(Mg0.2Co0.2Ni0.4Zn0.2)0,65O,
Li0,35(Mg0.2Co0.2Ni0.4Zn0.2)0,65O,
Na0,3(Mg0.2Co0.4Ni0.2Zn0.2)0,7O,
Li0,3(Mg0.2Co0.4Ni0.2Zn0.2)0,7O,
Na0,35(Mg0.2Co0.4Ni0.2Zn0.2)0,65O,
Li0,35(Mg0.2Co0.4Ni0.2Zn0.2)0,65O,
Na0,3(Mg0.4Co0.2Ni0.2Zn0.2)0,7O,
Li0,3(Mg0.4Co0.2Ni0.2Zn0.2)0,7O,
Na0,35(Mg0.4Co0.2Ni0.2Zn0.2)0,65O,
Li0,35(Mg0.4Co0.2Ni0.2Zn0.2)0,65O,
Na0,3(Mg0.25Co0.25Ni0.25Zn0.25)0,7O,
Li0,3(Mg0.25Co0.25Ni0.25Zn0.25)0,7O,
Na0,35(Mg0.25Co0.25Ni0.25Zn0.25)0,65O,
Li0,35(Mg0.25Co0.25Ni0.25Zn0.25)0,65O,
Na0,3(Mg0.2Co0.2Ni0.2Cu0.4)0,7O,
Li0,3(Mg0.2Co0.2Ni0.2Cu0.4)0,7O,
Na0,35(Mg0.2Co0.2Ni0.2Cu0.4)0,65O,
Li0,35(Mg0.2Co0.2Ni0.2Cu0.4)0,65O,
Na0,3(Mg0.2Co0.2Ni0.4Cu0.2)0,7O,
Li0,3(Mg0.2Co0.2Ni0.4Cu0.2)0,7O,
Na0,35(Mg0.2Co0.2Ni0.4Cu0.2)0,65O,
Li0,35(Mg0.2Co0.2Ni0.4Cu0.2)0,65O,
Na0,3(Mg0.2Co0.4Ni0.2Cu0.2)0,7O,
Li0,3(Mg0.2Co0.4Ni0.2Cu0.2)0,7O,
Na0,35(Mg0.2Co0.4Ni0.2Cu0.2)0,65O,
Li0,35(Mg0.2Co0.4Ni0.2Cu0.2)0,65O,
Na0,3(Mg0.4Co0.2Ni0.2Cu0.2)0,7O,
Li0,3(Mg0.4Co0.2Ni0.2Cu0.2)0,7O,
Na0,35(Mg0.4Co0.2Ni0.2Cu0.2)0,65O,
Li0,35(Mg0.4Co0.2Ni0.2Cu0.2)0,65O,
Na0,3(Mg0.25Co0.25Ni0.25Cu0.25)0,7O,
Li0,3(Mg0.25Co0.25Ni0.25Cu0.25)0,7O,
Na0,35(Mg0.25Co0.25Ni0.25Cu0.25)0,65O,
Li0,35(Mg0.25Co0.25Ni0.25Cu0.25)0,65O,
Na0,3(Mg0.2Co0.2Cu0.2Zn0.4)0,7O,
Li0,3(Mg0.2Co0.2Cu0.2Zn0.4)0,7O,
Na0,35(Mg0.2Co0.2Cu0.2Zn0.4)0,65O,
Li0,35(Mg0.2Co0.2Cu0.2Zn0.4)0,65O,
Na0,3(Mg0.2Co0.2Cu0.4Zn0.2)0,7O,
Li0,3(Mg0.2Co0.2Cu0.4Zn0.2)0,7O,
Na0,35(Mg0.2Co0.2Cu0.4Zn0.2)0,65O,
Li0,35(Mg0.2Co0.2Cu0.4Zn0.2)0,65O,
Na0,3(Mg0.2Co0.4Cu0.2Zn0.2)0,7O,
Li0,3(Mg0.2Co0.4Cu0.2Zn0.2)0,7O,
Na0,35(Mg0.2Co0.4Cu0.2Zn0.2)0,65O,
Li0,35(Mg0.2Co0.4Cu0.2Zn0.2)0,65O,
Na0,3(Mg0.4Co0.2Cu0.2Zn0.2)0,7O,
Li0,3(Mg0.4Co0.2Cu0.2Zn0.2)0,7O,
Na0,35(Mg0.4Co0.2Cu0.2Zn0.2)0,65O,
Li0,35(Mg0.4Co0.2Cu0.2Zn0.2)0,65O,
Na0,3(Mg0.25Co0.25Cu0.25Zn0.25)0,7O,
Li0,3(Mg0.25Co0.25Cu0.25Zn0.25)0,7O,
Na0,35(Mg0.25Co0.25Cu0.25Zn0.25)0,65O,
Li0,35(Mg0.25Co0.25Cu0.25Zn0.25)0,65O,
Na0,3(Co0.2Ni0.2Cu0.4Zn0.2)0,7O,
Li0,3(Co0.2Ni0.2Cu0.4Zn0.2)0,7O,
Na0,35(Co0.2Ni0.2Cu0.4Zn0.2)0,65O,
Li0,35(Co0.2Ni0.2Cu0.4Zn0.2)0,65O,
Na0,3(Co0.2Ni0.4Cu0.2Zn0.2)0,7O,
Li0,3(Co0.2Ni0.4Cu0.2Zn0.2)0,7O,
Na0,35(Co0.2Ni0.4Cu0.2Zn0.2)0,65O,
Li0,35(Co0.2Ni0.4ZCu0.2Zn0.2)0,65O,
Na0,3(Co0.4Ni0.2Cu0.2Zn0.2)0,7O,
Li0,3(Co0.4Ni0.2Cu0.2Zn0.2)0,7O,
Na0,35(Co0.4Ni0.2Cu0.2Zn0.2)0,65O,
Li0,35(Co0.4Ni0.2Cu0.2Zn0.2)0,65O,
Na0,3(Co0.2Ni0.2Cu0.2Zn0.4)0,7O,
Li0,3(Co0.2Ni0.2Cu0.2Zn0.4)0,7O,
Na0,35(Co0.2Ni0.2Cu0.2Zn0.4)0,65O,
Li0,35(Co0.2Ni0.2Cu0.2Zn0.4)0,65O,
Na0,3(Co0.25Ni0.25Cu0.25Zn0.25)0,7O,
Li0,3(Co0.25Ni0.25Cu0.25Zn0.25)0,7O,
Na0,35(Co0.25Ni0.25Cu0.25Zn0.25)0,65O,
Li0,35(Co0.25Ni0.25Cu0.25Zn0.25)0,65O,
Na0,3(Mg0.2Ni0.2Cu0.4Zn0.2)0,7O,
Li0,3(Mg0.2Ni0.2Cu0.4Zn0.2)0,7O,
Na0,35(Mg0.2Ni0.2Cu0.4Zn0.2)0,65O,
Li0,35(Mg0.2Ni0.2Cu0.4Zn0.2)0,65O,
Na0,3(Mg0.2Ni0.4Cu0.2Zn0.2)0,7O,
Li0,3(Mg0.2Ni0.4Cu0.2Zn0.2)0,7O,
Na0,35(Mg0.2Ni0.4Cu0.2Zn0.2)0,65O,
Li0,35(Mg0.2Ni0.4ZCu0.2Zn0.2)0,65O,
Na0,3(Mg0.4Ni0.2Cu0.2Zn0.2)0,7O,
Li0,3(Mg0.4Ni0.2Cu0.2Zn0.2)0,7O,
Na0,35(Mg0.4Ni0.2Cu0.2Zn0.2)0,65O,
Li0,35(Mg0.4Ni0.2Cu0.2Zn0.2)0,65O,
Na0,3(Mg0.2Ni0.2Cu0.2Zn0.4)0,7O,
Li0,3(Mg0.2Ni0.2Cu0.2Zn0.4)0,7O,
Na0,35(Mg0.2Ni0.2Cu0.2Zn0.4)0,65O,
Li0,35(Mg0.2Ni0.2Cu0.2Zn0.4)0,65O,
Na0,3(Mg0.25Ni0.25Cu0.25Zn0.25)0,7O,
Li0,3(Mg0.25Ni0.25Cu0.25Zn0.25)0,7O,
Na0,35(Mg0.25Ni0.25Cu0.25Zn0.25)0,65O et
Li0,35(Mg0.25Ni0.25Cu0.25Zn0.25)0,65OPreferably, the high-entropy oxide is chosen from
Na 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Zn 0.4 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Zn 0.4 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Zn 0.4 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Zn 0.4 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.2 Ni 0.4 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Ni 0.4 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Ni 0.4 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Ni 0.4 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.4 Ni 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.4 Ni 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.4 Ni 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.4 Ni 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.4 Co 0.2 Ni 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.4 Co 0.2 Ni 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.4 Co 0.2 Ni 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.4 Co 0.2 Ni 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.25 Co 0.25 Ni 0.25 Zn 0.25 ) 0.7 O,
Li 0.3 (Mg 0.25 Co 0.25 Ni 0.25 Zn 0.25 ) 0.7 O,
Na 0.35 (Mg 0.25 Co 0.25 Ni 0.25 Zn 0.25 ) 0.65 O,
Li 0.35 (Mg 0.25 Co 0.25 Ni 0.25 Zn 0.25 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.4 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.4 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.4 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.4 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.2 Ni 0.4 Cu 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Ni 0.4 Cu 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Ni 0.4 Cu 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Ni 0.4 Cu 0.2 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.4 Ni 0.2 Cu 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.4 Ni 0.2 Cu 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.4 Ni 0.2 Cu 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.4 Ni 0.2 Cu 0.2 ) 0.65 O,
Na 0.3 (Mg 0.4 Co 0.2 Ni 0.2 Cu 0.2 ) 0.7 O,
Li 0.3 (Mg 0.4 Co 0.2 Ni 0.2 Cu 0.2 ) 0.7 O,
Na 0.35 (Mg 0.4 Co 0.2 Ni 0.2 Cu 0.2 ) 0.65 O,
Li 0.35 (Mg 0.4 Co 0.2 Ni 0.2 Cu 0.2 ) 0.65 O,
Na 0.3 (Mg 0.25 Co 0.25 Ni 0.25 Cu 0.25 ) 0.7 O,
Li 0.3 (Mg 0.25 Co 0.25 Ni 0.25 Cu 0.25 ) 0.7 O,
Na 0.35 (Mg 0.25 Co 0.25 Ni 0.25 Cu 0.25 ) 0.65 O,
Li 0.35 (Mg 0.25 Co 0.25 Ni 0.25 Cu 0.25 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.4 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.4 Cu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.4 Co 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.4 Co 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.4 Co 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.4 Co 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.25 Co 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Li 0.3 (Mg 0.25 Co 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Na 0.35 (Mg 0.25 Co 0.25 Cu 0.25 Zn 0.25 ) 0.65 O,
Li 0.35 (Mg 0.25 Co 0.25 Cu 0.25 Zn 0.25 ) 0.65 O,
Na 0.3 (Co 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Li 0.3 (Co 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Na 0.35 (Co 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Li 0.35 (Co 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Na 0.3 (Co 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Co 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Co 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Co 0.2 Ni 0.4 ZCu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Co 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Co 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Co 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Co 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Co 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Li 0.3 (Co 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Na 0.35 (Co 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Li 0.35 (Co 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Na 0.3 (Co 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Li 0.3 (Co 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Na 0.35 (Co 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.65 O,
Li 0.35 (Co 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.65 O,
Na 0.3 (Mg 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Ni 0.4 ZCu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Li 0.3 (Mg 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Na 0.35 (Mg 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Li 0.35 (Mg 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Na 0.3 (Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Li 0.3 (Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Na 0.35 (Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.65 O and
Li 0.35 (Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.65 O

L’invention a également pour objet l’utilisation d’un oxyde à haute tel que décrit ci-dessus en tant qu’électrolyte solide conducteur des ions du métal alcalin A.A subject of the invention is also the use of a high oxide as described above as a solid electrolyte which conducts ions of the alkali metal A.

L’invention a également pour objet une batterie rechargeable inorganique solide comprenant :The invention also relates to a solid inorganic rechargeable battery comprising:

  • une anode solide (1) comprenant un métal alcalin (A) ou un alliage de métal alcalin (A)a solid anode (1) comprising an alkali metal (A) or an alkali metal alloy (A)
  • une cathode solide (2) comprenant un composé d’insertion des ions de métal alcalin (A), ladite cathode (2) étant dépourvue de polymèrea solid cathode (2) comprising an alkali metal ion insertion compound (A), said cathode (2) being free of polymer
  • une couche solide (3), positionnée entre l’anode (1) et la cathode (2), comprenant un électrolyte solide conducteur des ions de métal alcalin (A), ledit électrolyte solide comprenant un oxyde à haute entropie de formule (I) tel que décrit ci-dessus.a solid layer (3), positioned between the anode (1) and the cathode (2), comprising a solid electrolyte which conducts alkali metal ions (A), said solid electrolyte comprising a high entropy oxide of formula (I) as described above.

Préférentiellement, le métal alcalin de l’anode (1) est le sodium ou le lithium, de façon préférée le sodium.Preferably, the alkali metal of the anode (1) is sodium or lithium, preferably sodium.

Préférentiellement, le composé d’insertion de la cathode (2) est choisi parmi les oxydes, les phosphates et leurs mélanges.Preferably, the cathode insertion compound (2) is chosen from oxides, phosphates and mixtures thereof.

Préférentiellement, le composé d’insertion de la cathode (2) est choisi parmi Na0.7MnO2, NaCoO2, NaTiO2, NaV2O5, NaFePO4, NaCrO3et leurs mélanges.Preferably, the cathode insertion compound (2) is chosen from Na 0.7 MnO 2 , NaCoO 2 , NaTiO 2 , NaV 2 O 5 , NaFePO 4 , NaCrO 3 and their mixtures.

Préférentiellement, la cathode (2) comprend en outre un oxyde à haute entropie conducteur des ions dudit métal alcalin, de formule (II) :Preferably, the cathode (2) further comprises a high-entropy oxide conductor of the ions of said alkali metal, of formula (II):

AyM’1-yO (II) où :A y M' 1-y O (II) where:

  • A désigne le métal alcalinA denotes the alkali metal
  • M’ est une combinaison d’éléments métalliques comprenant au moins 4 éléments choisis parmi le Mg, le Co, le Ni, le Cu et le ZnM' is a combination of metallic elements comprising at least 4 elements chosen from among Mg, Co, Ni, Cu and Zn
  • y est la fraction molaire en métal alcalin A par rapport à la combinaison d’éléments métalliques M’ et au métal alcalin A, et est comprise entre 0,15 et 0,35, de préférence entre 0,30 et 0,35y is the molar fraction of alkali metal A with respect to the combination of metallic elements M' and the alkali metal A, and is between 0.15 and 0.35, preferably between 0.30 and 0.35
  • O désigne l’oxygène.O stands for oxygen.

Préférentiellement, l’oxyde à haute entropie de la cathode (2) est de même composition que l’oxyde à haute entropie de la couche (3).Preferably, the high entropy oxide of the cathode (2) has the same composition as the high entropy oxide of the layer (3).

Préférentiellement, la cathode (2) comprend en outre du graphite.Preferably, the cathode (2) further comprises graphite.

Préférentiellement, la batterie massive est une batterie massive ou une micro-batterie couche mince.Preferably, the massive battery is a massive battery or a thin layer micro-battery.

L’invention a également pour objet l’utilisation d’une batterie rechargeable inorganique solide telle que décrite ci-dessus dont les opérations de charge et de décharge s’effectuent à une température comprise entre - 20°C et 100°C, de préférence entre 10°C et 40°C, de façon particulièrement préférée entre 15°C et 25°C.The invention also relates to the use of a solid inorganic rechargeable battery as described above, the charging and discharging operations of which are carried out at a temperature between - 20° C. and 100° C., preferably between 10°C and 40°C, particularly preferably between 15°C and 25°C.

L’invention a également pour objet un véhicule comportant une batterie rechargeable inorganique solide massive telle que décrite ci-dessus configurée pour stocker et alimenter ledit véhicule en énergie.The invention also relates to a vehicle comprising a massive solid inorganic rechargeable battery as described above configured to store and supply said vehicle with energy.

L’invention a également pour objet un appareil électronique autonome de type objet connecté comportant une batterie rechargeable inorganique solide massive ou une microbatterie telles que décrites ci-dessus configurée pour stocker et alimenter ledit appareil en énergie.The invention also relates to an autonomous electronic device of the connected object type comprising a massive solid inorganic rechargeable battery or a microbattery as described above configured to store and supply said device with energy.

L’invention a également pour objet un réseau intelligent d’électricité de type Smart Grid comportant une batterie rechargeable inorganique solide massive telle que décrite ci-dessus configurée pour stocker et alimenter ledit réseau en énergie.The invention also relates to an intelligent electricity network of the Smart Grid type comprising a massive solid inorganic rechargeable battery as described above configured to store and supply said network with energy.

DESCRIPTION DES FIGURESDESCRIPTION OF FIGURES

: représente l’évolution de la conductivité ionique d’un oxyde à haute entropie de formule Ax(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)1-xO avec A = Li ou Na, en fonction de la fraction molaire x de métal alcalin comprise entre 0 et 0,32, à 20°C et 80°C (exemple 3) : represents the evolution of the ionic conductivity of a high entropy oxide of formula A x (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 1-x O with A = Li or Na, depending on the molar fraction x of alkali metal between 0 and 0.32, at 20° C. and 80° C. (Example 3)

: représente le diffractogramme de rayons X pour l’oxyde à haute entropie de formule Na0,4(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)0,6O selon l’exemple 3. L’oxyde à haute entropie est donc de formule (I) AxM1-xO telle que définie dans le texte avec x=0,4. : represents the X-ray diffractogram for the high entropy oxide of formula Na 0.4 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.6 O according to example 3. The high entropy oxide is therefore of formula (I) A x M 1 -x O as defined in the text with x=0.4.

: représente le diffractogramme de rayons X pour l’oxyde à haute entropie de formule Na0,32(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)0,68O selon l’exemple 3. L’oxyde à haute entropie est donc de formule (I) AxM1-xO telle que définie dans le texte avec x=0,32. : represents the X-ray diffractogram for the high entropy oxide of formula Na 0.32 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.68 O according to example 3. The high entropy oxide is therefore of formula (I) A x M 1 -x O as defined in the text with x=0.32.

: représente, de haut en bas, le diffractogramme de rayons X de l’oxyde à haute entropie de formule Li0.166(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)0.834O à l’état initial (diffractogramme du haut) , après 1 mois à température ambiante sous air (diffractogramme du milieu) et après 24h à température ambiante dans l’eau (diffractogramme du bas) selon l’exemple 4. L’oxyde à haute entropie est donc de formule (I) AxM1-xO telle que définie dans le texte avec x=0,166. : represents, from top to bottom, the X-ray diffractogram of the high entropy oxide of formula Li 0.166 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.834 O in the initial state (top diffractogram), after 1 month at room temperature in air (middle diffractogram) and after 24 hours at room temperature in water (bottom diffractogram) according to example 4. The high entropy oxide is therefore of formula (I) A x M 1 -x O as defined in the text with x=0.166.

: schématise les étapes de fabrication et d’assemblage de la cathode (2) et de la couche d’électrolyte (3) dans une batterie massive selon l’invention, l’étape (I) correspondant à l’insertion des composants des couches individuelles sous forme de poudre, l’étape (II) étant l’étape de compactage des 2 couches simultanément : diagrams the steps for manufacturing and assembling the cathode (2) and the electrolyte layer (3) in a bulk battery according to the invention, step (I) corresponding to the insertion of the components of the layers individual in powder form, step (II) being the step of compacting the 2 layers simultaneously

: représente l’interface entre la cathode (2) et la couche (3) après l’étape d’assemblage (iii) illustrée sur la de l’exemple 6. : represents the interface between the cathode (2) and the layer (3) after the assembly step (iii) illustrated on the of Example 6.

: schématise les étapes de fabrication et d’assemblage de la cathode (2) et de la couche d’électrolyte (3) dans une batterie massive selon l’invention selon un procédé alternatif à celui de la . L’étape (I) correspond au compactage des couches individuelles, séparément. L’étape (II) correspond à l’assemblage des 2 couches individuelles et à leur compactage. : schematizes the steps for manufacturing and assembling the cathode (2) and the electrolyte layer (3) in a bulk battery according to the invention according to an alternative method to that of the . Stage (I) corresponds to the compaction of the individual layers, separately. Step (II) corresponds to the assembly of the 2 individual layers and their compaction.

: démontre l’absence d’auto-décharge et/ou de court-circuit sur 5h pour la cellule selon l’exemple 7.2 ayant la configuration suivante : électrode positive à base de Nickel – Manganèse – Cobalt (NMC) - carbone graphite - oxyde à haute entropie/oxyde à haute entropie/lithium : demonstrates the absence of self-discharge and/or short-circuit over 5h for the cell according to example 7.2 having the following configuration: positive electrode based on Nickel – Manganese – Cobalt (NMC) - graphite carbon - oxide high entropy/oxide high entropy/lithium

: représente les données de cyclage E (V /Li) en fonction du temps t à faible régime (C/100) pour la cellule selon l’exemple 7.2 ayant la configuration suivante : électrode positive à base de Nickel – Manganèse – Cobalt (NMC) - carbone graphite - oxyde à haute entropie/oxyde à haute entropie/lithium : represents the cycling data E (V /Li) as a function of time t at low speed (C/100) for the cell according to example 7.2 having the following configuration: positive electrode based on Nickel – Manganese – Cobalt (NMC ) - carbon graphite - high entropy oxide/high entropy oxide/lithium

: représente les données de cyclage E (V /Na) en fonction du temps t à faible régime (C/100) pour la cellule selon l’exemple 7.2 ayant la configuration suivante : électrode positive à base de NaCoO2- carbone graphite - oxyde à haute entropie/oxyde à haute entropie/Na métal : represents the cycling data E (V /Na) as a function of time t at low speed (C/100) for the cell according to example 7.2 having the following configuration: positive electrode based on NaCoO 2 - graphite carbon - oxide high entropy/high entropy oxide/Na metal

: représente la rétention de capacité en fonction du nombre de cycles N de charge/décharge de la cellule selon l’exemple 7.2 ayant la configuration suivante : électrode positive à base de NaCoO2- carbone graphite - oxyde à haute entropie/oxyde à haute entropie/Na métal : represents the capacity retention as a function of the number of charge/discharge cycles N of the cell according to example 7.2 having the following configuration: positive electrode based on NaCoO 2 - graphite carbon - high entropy oxide/high entropy oxide /Na metal

: représente les données de cyclage E (V /Na) en fonction du temps t à faible régime (C/100) pour la cellule selon l’exemple 7.2 ayant la configuration suivante: électrode positive à base de Na0.7MnO2- carbone graphite - oxyde à haute entropie/oxyde à haute entropie/Na métal : represents the cycling data E (V /Na) as a function of time t at low speed (C/100) for the cell according to example 7.2 having the following configuration: positive electrode based on Na 0.7 MnO 2 - graphite carbon - high entropy oxide/high entropy oxide/Na metal

: représente la rétention de capacité en fonction du nombre de cycles N de charge/décharge de la cellule selon l’exemple 7.2 ayant la configuration suivante : électrode positive à base de LiMnO2- carbone graphite - oxyde à haute entropie/oxyde à haute entropie/Li métal : represents the capacity retention as a function of the number of charge/discharge cycles N of the cell according to example 7.2 having the following configuration: positive electrode based on LiMnO 2 - graphite carbon - high entropy oxide/high entropy oxide /Li metal

Claims (19)

Procédé de préparation d’un oxyde à haute entropie de formule (I) :
● AxM1-xO (I) où :
o A désigne un métal alcalin ;
o M est une combinaison d’éléments métalliques comprenant au moins 4 éléments choisis parmi le Mg, le Co, le Ni, le Cu et le Zn ;
o x est la fraction molaire en métal alcalin A par rapport à la combinaison d’éléments métalliques M et au métal alcalin A, et est comprise entre 0,15 et 0,35, de préférence entre 0,30 et 0,35 ;
o et O désigne l’oxygène ;
● comprenant les étapes successives suivantes, à partir d’un mélange broyé et compacté d’oxydes binaires des éléments métalliques de M et de carbonate alcalin source de A :
o chauffage du mélange compacté à une température supérieure à 900°C sous air, puis ;
o trempe sous pression partielle d’oxygène Pox telle que 0 Pa ≤ Pox < 2*104Pa du mélange compacté issu de l’étape de chauffe.Process for the preparation of a high entropy oxide of formula (I):
● AxM1-xO (I) where:
o A denotes an alkali metal;
o M is a combination of metallic elements comprising at least 4 elements chosen from Mg, Co, Ni, Cu and Zn;
o x is the molar fraction of alkali metal A relative to the combination of metallic elements M and to the alkali metal A, and is between 0.15 and 0.35, preferably between 0.30 and 0.35;
o and O designate oxygen;
● comprising the following successive steps, from a crushed and compacted mixture of binary oxides of the metallic elements of M and alkali carbonate source of A:
o heating of the compacted mixture to a temperature above 900° C. in air, then;
o quenching under partial pressure of oxygen Pox such that 0 Pa ≤ Pox < 2*104Pa of the compacted mixture from the heating step. Oxyde à haute entropie de formule (I) tel que défini dans la revendication 1 caractérisé en ce que sa conductivité est essentiellement de nature ionique.High-entropy oxide of formula (I) as defined in claim 1, characterized in that its conductivity is essentially ionic in nature. Oxyde à haute entropie selon la revendication 2 caractérisé en ce que M est une combinaison des 5 éléments métalliques suivants : le Mg, le Co, le Ni, le Cu et le Zn.High entropy oxide according to Claim 2, characterized in that M is a combination of the following 5 metallic elements: Mg, Co, Ni, Cu and Zn. Oxyde à haute entropie selon la revendication 3 choisi parmi
Na0.3(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)0.7O, Li0.3(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)0.7O,
Na0.35(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)0.65O et Li0.35(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)0.65O.High-entropy oxide according to claim 3 chosen from
Na 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O, Li 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O and Li 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O. Oxyde à haute entropie selon la revendication 2 caractérisé en ce que M est une combinaison de 4 éléments métalliques choisis parmi le Mg, le Co, le Ni, le Cu et le Zn.High entropy oxide according to Claim 2, characterized in that M is a combination of 4 metallic elements chosen from Mg, Co, Ni, Cu and Zn. Oxyde à haute entropie selon la revendication 5 choisi parmi
Na0,3(Mg0.2Co0.2Ni0.2Zn0.4)0,7O,
Li0,3(Mg0.2Co0.2Ni0.2Zn0.4)0,7O,
Na0,35(Mg0.2Co0.2Ni0.2Zn0.4)0,65O,
Li0,35(Mg0.2Co0.2Ni0.2Zn0.4)0,65O,
Na0,3(Mg0.2Co0.2Ni0.4Zn0.2)0,7O,
Li0,3(Mg0.2Co0.2Ni0.4Zn0.2)0,7O,
Na0,35(Mg0.2Co0.2Ni0.4Zn0.2)0,65O,
Li0,35(Mg0.2Co0.2Ni0.4Zn0.2)0,65O,
Na0,3(Mg0.2Co0.4Ni0.2Zn0.2)0,7O,
Li0,3(Mg0.2Co0.4Ni0.2Zn0.2)0,7O,
Na0,35(Mg0.2Co0.4Ni0.2Zn0.2)0,65O,
Li0,35(Mg0.2Co0.4Ni0.2Zn0.2)0,65O,
Na0,3(Mg0.4Co0.2Ni0.2Zn0.2)0,7O,
Li0,3(Mg0.4Co0.2Ni0.2Zn0.2)0,7O,
Na0,35(Mg0.4Co0.2Ni0.2Zn0.2)0,65O,
Li0,35(Mg0.4Co0.2Ni0.2Zn0.2)0,65O,
Na0,3(Mg0.25Co0.25Ni0.25Zn0.25)0,7O,
Li0,3(Mg0.25Co0.25Ni0.25Zn0.25)0,7O,
Na0,35(Mg0.25Co0.25Ni0.25Zn0.25)0,65O,
Li0,35(Mg0.25Co0.25Ni0.25Zn0.25)0,65O,
Na0,3(Mg0.2Co0.2Ni0.2Cu0.4)0,7O,
Li0,3(Mg0.2Co0.2Ni0.2Cu0.4)0,7O,
Na0,35(Mg0.2Co0.2Ni0.2Cu0.4)0,65O,
Li0,35(Mg0.2Co0.2Ni0.2Cu0.4)0,65O,
Na0,3(Mg0.2Co0.2Ni0.4Cu0.2)0,7O,
Li0,3(Mg0.2Co0.2Ni0.4Cu0.2)0,7O,
Na0,35(Mg0.2Co0.2Ni0.4Cu0.2)0,65O,
Li0,35(Mg0.2Co0.2Ni0.4Cu0.2)0,65O,
Na0,3(Mg0.2Co0.4Ni0.2Cu0.2)0,7O,
Li0,3(Mg0.2Co0.4Ni0.2Cu0.2)0,7O,
Na0,35(Mg0.2Co0.4Ni0.2Cu0.2)0,65O,
Li0,35(Mg0.2Co0.4Ni0.2Cu0.2)0,65O,
Na0,3(Mg0.4Co0.2Ni0.2Cu0.2)0,7O,
Li0,3(Mg0.4Co0.2Ni0.2Cu0.2)0,7O,
Na0,35(Mg0.4Co0.2Ni0.2Cu0.2)0,65O,
Li0,35(Mg0.4Co0.2Ni0.2Cu0.2)0,65O,
Na0,3(Mg0.25Co0.25Ni0.25Cu0.25)0,7O,
Li0,3(Mg0.25Co0.25Ni0.25Cu0.25)0,7O,
Na0,35(Mg0.25Co0.25Ni0.25Cu0.25)0,65O,
Li0,35(Mg0.25Co0.25Ni0.25Cu0.25)0,65O,
Na0,3(Mg0.2Co0.2Cu0.2Zn0.4)0,7O,
Li0,3(Mg0.2Co0.2Cu0.2Zn0.4)0,7O,
Na0,35(Mg0.2Co0.2Cu0.2Zn0.4)0,65O,
Li0,35(Mg0.2Co0.2Cu0.2Zn0.4)0,65O,
Na0,3(Mg0.2Co0.2Cu0.4Zn0.2)0,7O,
Li0,3(Mg0.2Co0.2Cu0.4Zn0.2)0,7O,
Na0,35(Mg0.2Co0.2Cu0.4Zn0.2)0,65O,
Li0,35(Mg0.2Co0.2Cu0.4Zn0.2)0,65O,
Na0,3(Mg0.2Co0.4Cu0.2Zn0.2)0,7O,
Li0,3(Mg0.2Co0.4Cu0.2Zn0.2)0,7O,
Na0,35(Mg0.2Co0.4Cu0.2Zn0.2)0,65O,
Li0,35(Mg0.2Co0.4Cu0.2Zn0.2)0,65O,
Na0,3(Mg0.4Co0.2Cu0.2Zn0.2)0,7O,
Li0,3(Mg0.4Co0.2Cu0.2Zn0.2)0,7O,
Na0,35(Mg0.4Co0.2Cu0.2Zn0.2)0,65O,
Li0,35(Mg0.4Co0.2Cu0.2Zn0.2)0,65O,
Na0,3(Mg0.25Co0.25Cu0.25Zn0.25)0,7O,
Li0,3(Mg0.25Co0.25Cu0.25Zn0.25)0,7O,
Na0,35(Mg0.25Co0.25Cu0.25Zn0.25)0,65O,
Li0,35(Mg0.25Co0.25Cu0.25Zn0.25)0,65O,
Na0,3(Co0.2Ni0.2Cu0.4Zn0.2)0,7O,
Li0,3(Co0.2Ni0.2Cu0.4Zn0.2)0,7O,
Na0,35(Co0.2Ni0.2Cu0.4Zn0.2)0,65O,
Li0,35(Co0.2Ni0.2Cu0.4Zn0.2)0,65O,
Na0,3(Co0.2Ni0.4Cu0.2Zn0.2)0,7O,
Li0,3(Co0.2Ni0.4Cu0.2Zn0.2)0,7O,
Na0,35(Co0.2Ni0.4Cu0.2Zn0.2)0,65O,
Li0,35(Co0.2Ni0.4ZCu0.2Zn0.2)0,65O,
Na0,3(Co0.4Ni0.2Cu0.2Zn0.2)0,7O,
Li0,3(Co0.4Ni0.2Cu0.2Zn0.2)0,7O,
Na0,35(Co0.4Ni0.2Cu0.2Zn0.2)0,65O,
Li0,35(Co0.4Ni0.2Cu0.2Zn0.2)0,65O,
Na0,3(Co0.2Ni0.2Cu0.2Zn0.4)0,7O,
Li0,3(Co0.2Ni0.2Cu0.2Zn0.4)0,7O,
Na0,35(Co0.2Ni0.2Cu0.2Zn0.4)0,65O,
Li0,35(Co0.2Ni0.2Cu0.2Zn0.4)0,65O,
Na0,3(Co0.25Ni0.25Cu0.25Zn0.25)0,7O,
Li0,3(Co0.25Ni0.25Cu0.25Zn0.25)0,7O,
Na0,35(Co0.25Ni0.25Cu0.25Zn0.25)0,65O,
Li0,35(Co0.25Ni0.25Cu0.25Zn0.25)0,65O,
Na0,3(Mg0.2Ni0.2Cu0.4Zn0.2)0,7O,
Li0,3(Mg0.2Ni0.2Cu0.4Zn0.2)0,7O,
Na0,35(Mg0.2Ni0.2Cu0.4Zn0.2)0,65O,
Li0,35(Mg0.2Ni0.2Cu0.4Zn0.2)0,65O,
Na0,3(Mg0.2Ni0.4Cu0.2Zn0.2)0,7O,
Li0,3(Mg0.2Ni0.4Cu0.2Zn0.2)0,7O,
Na0,35(Mg0.2Ni0.4Cu0.2Zn0.2)0,65O,
Li0,35(Mg0.2Ni0.4ZCu0.2Zn0.2)0,65O,
Na0,3(Mg0.4Ni0.2Cu0.2Zn0.2)0,7O,
Li0,3(Mg0.4Ni0.2Cu0.2Zn0.2)0,7O,
Na0,35(Mg0.4Ni0.2Cu0.2Zn0.2)0,65O,
Li0,35(Mg0.4Ni0.2Cu0.2Zn0.2)0,65O,
Na0,3(Mg0.2Ni0.2Cu0.2Zn0.4)0,7O,
Li0,3(Mg0.2Ni0.2Cu0.2Zn0.4)0,7O,
Na0,35(Mg0.2Ni0.2Cu0.2Zn0.4)0,65O,
Li0,35(Mg0.2Ni0.2Cu0.2Zn0.4)0,65O,
Na0,3(Mg0.25Ni0.25Cu0.25Zn0.25)0,7O,
Li0,3(Mg0.25Ni0.25Cu0.25Zn0.25)0,7O,
Na0,35(Mg0.25Ni0.25Cu0.25Zn0.25)0,65O et
Li0,35(Mg0.25Ni0.25Cu0.25Zn0.25)0,65O.High-entropy oxide according to claim 5 selected from
Na 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Zn 0.4 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Zn 0.4 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Zn 0.4 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Zn 0.4 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.2 Ni 0.4 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Ni 0.4 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Ni 0.4 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Ni 0.4 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.4 Ni 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.4 Ni 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.4 Ni 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.4 Ni 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.4 Co 0.2 Ni 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.4 Co 0.2 Ni 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.4 Co 0.2 Ni 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.4 Co 0.2 Ni 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.25 Co 0.25 Ni 0.25 Zn 0.25 ) 0.7 O,
Li 0.3 (Mg 0.25 Co 0.25 Ni 0.25 Zn 0.25 ) 0.7 O,
Na 0.35 (Mg 0.25 Co 0.25 Ni 0.25 Zn 0.25 ) 0.65 O,
Li 0.35 (Mg 0.25 Co 0.25 Ni 0.25 Zn 0.25 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.4 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.4 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.4 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.4 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.2 Ni 0.4 Cu 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Ni 0.4 Cu 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Ni 0.4 Cu 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Ni 0.4 Cu 0.2 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.4 Ni 0.2 Cu 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.4 Ni 0.2 Cu 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.4 Ni 0.2 Cu 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.4 Ni 0.2 Cu 0.2 ) 0.65 O,
Na 0.3 (Mg 0.4 Co 0.2 Ni 0.2 Cu 0.2 ) 0.7 O,
Li 0.3 (Mg 0.4 Co 0.2 Ni 0.2 Cu 0.2 ) 0.7 O,
Na 0.35 (Mg 0.4 Co 0.2 Ni 0.2 Cu 0.2 ) 0.65 O,
Li 0.35 (Mg 0.4 Co 0.2 Ni 0.2 Cu 0.2 ) 0.65 O,
Na 0.3 (Mg 0.25 Co 0.25 Ni 0.25 Cu 0.25 ) 0.7 O,
Li 0.3 (Mg 0.25 Co 0.25 Ni 0.25 Cu 0.25 ) 0.7 O,
Na 0.35 (Mg 0.25 Co 0.25 Ni 0.25 Cu 0.25 ) 0.65 O,
Li 0.35 (Mg 0.25 Co 0.25 Ni 0.25 Cu 0.25 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.2 Co 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Co 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Co 0.4 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Co 0.4 Cu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.4 Co 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.4 Co 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.4 Co 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.4 Co 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.25 Co 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Li 0.3 (Mg 0.25 Co 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Na 0.35 (Mg 0.25 Co 0.25 Cu 0.25 Zn 0.25 ) 0.65 O,
Li 0.35 (Mg 0.25 Co 0.25 Cu 0.25 Zn 0.25 ) 0.65 O,
Na 0.3 (Co 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Li 0.3 (Co 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Na 0.35 (Co 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Li 0.35 (Co 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Na 0.3 (Co 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Co 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Co 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Co 0.2 Ni 0.4 ZCu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Co 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Co 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Co 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Co 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Co 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Li 0.3 (Co 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Na 0.35 (Co 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Li 0.35 (Co 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Na 0.3 (Co 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Li 0.3 (Co 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Na 0.35 (Co 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.65 O,
Li 0.35 (Co 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.65 O,
Na 0.3 (Mg 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Ni 0.2 Cu 0.4 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.2 Ni 0.4 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.2 Ni 0.4 ZCu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Li 0.3 (Mg 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.7 O,
Na 0.35 (Mg 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Li 0.35 (Mg 0.4 Ni 0.2 Cu 0.2 Zn 0.2 ) 0.65 O,
Na 0.3 (Mg 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Li 0.3 (Mg 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.7 O,
Na 0.35 (Mg 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Li 0.35 (Mg 0.2 Ni 0.2 Cu 0.2 Zn 0.4 ) 0.65 O,
Na 0.3 (Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Li 0.3 (Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.7 O,
Na 0.35 (Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.65 O and
Li 0.35 (Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 ) 0.65 O. Utilisation d’un oxyde à haute entropie selon l’une quelconque des revendications 2 à 6 en tant qu’électrolyte solide conducteur des ions du métal alcalin A.Use of a high-entropy oxide according to any one of Claims 2 to 6 as solid electrolyte which conducts ions of the alkali metal A. Batterie rechargeable inorganique solide comprenant :
- une anode solide (1) comprenant un métal alcalin (A) ou un alliage de métal alcalin (A)
- une cathode solide (2) comprenant un composé d’insertion des ions de métal alcalin (A), ladite cathode (2) étant dépourvue de polymère
- une couche solide (3), positionnée entre l’anode (1) et la cathode (2), comprenant un électrolyte solide conducteur des ions de métal alcalin (A), ledit électrolyte solide comprenant un oxyde à haute entropie de formule (I) tel que défini dans l’une quelconque des revendications 1 à 6.Solid inorganic rechargeable battery including:
- a solid anode (1) comprising an alkali metal (A) or an alkali metal alloy (A)
- a solid cathode (2) comprising an alkali metal ion insertion compound (A), said cathode (2) being devoid of polymer
- a solid layer (3), positioned between the anode (1) and the cathode (2), comprising a solid electrolyte which conducts alkali metal ions (A), said solid electrolyte comprising a high-entropy oxide of formula (I ) as defined in any one of claims 1 to 6. Batterie rechargeable inorganique solide selon la revendication 8 caractérisée en ce que le métal alcalin de ladite anode (1) est le sodium ou le lithium, de façon préférée le sodium.Solid inorganic rechargeable battery according to Claim 8, characterized in that the alkali metal of the said anode (1) is sodium or lithium, preferably sodium. Batterie rechargeable inorganique solide selon l’une quelconque des revendications 8 à 9 caractérisée en ce que le composé d’insertion de la cathode (2) est choisi parmi les oxydes, les phosphates et leurs mélanges.Solid inorganic rechargeable battery according to any one of Claims 8 to 9, characterized in that the cathode insertion compound (2) is chosen from oxides, phosphates and mixtures thereof. Batterie rechargeable inorganique solide selon la revendication 9 caractérisée en ce que le composé d’insertion de la cathode (2) est choisi parmi Na0.7MnO2, NaCoO2, NaTiO2, NaV2O5, NaFePO4, NaCrO3et leurs mélanges.Solid inorganic rechargeable battery according to Claim 9, characterized in that the compound for inserting the cathode (2) is chosen from Na 0.7 MnO 2 , NaCoO 2 , NaTiO 2 , NaV 2 O 5 , NaFePO 4 , NaCrO 3 and their mixtures . Batterie rechargeable inorganique solide selon l’une quelconque des revendications 8 à 11 caractérisée en ce que la cathode (2) comprend en outre un oxyde à haute entropie conducteur des ions dudit métal alcalin, de formule (II) :
AyM’1-yO (II) où :
- A désigne le métal alcalin
- M’ est une combinaison d’éléments métalliques comprenant au moins 4 éléments choisis parmi le Mg, le Co, le Ni, le Cu et le Zn
- y est la fraction molaire en métal alcalin A par rapport à la combinaison d’éléments métalliques M’ et au métal alcalin A, et est comprise entre 0,15 et 0,35, de préférence entre 0,30 et 0,35
- O désigne l’oxygène.Solid inorganic rechargeable battery according to any one of Claims 8 to 11, characterized in that the cathode (2) further comprises a high-entropy oxide conductor of the ions of the said alkali metal, of formula (II):
A y M' 1-y O (II) where:
- A denotes the alkali metal
- M' is a combination of metallic elements comprising at least 4 elements chosen from Mg, Co, Ni, Cu and Zn
- y is the molar fraction of alkali metal A relative to the combination of metallic elements M' and to the alkali metal A, and is between 0.15 and 0.35, preferably between 0.30 and 0.35
- O denotes oxygen. Batterie rechargeable inorganique solide selon la revendication 12 caractérisée en ce que l’oxyde à haute entropie de la cathode (2) est de même composition que l’oxyde à haute entropie de la couche (3).Solid inorganic rechargeable battery according to Claim 12, characterized in that the high entropy oxide of the cathode (2) has the same composition as the high entropy oxide of the layer (3). Batterie rechargeable inorganique solide selon l’une quelconque des revendications 8 à 13 caractérisée en ce que la cathode (2) comprend en outre du graphite.Solid inorganic rechargeable battery according to any one of Claims 8 to 13, characterized in that the cathode (2) further comprises graphite. Batterie rechargeable inorganique solide selon l’une quelconque des revendications 8 à 14 choisie parmi une batterie massive et une micro-batterie couche mince.Solid inorganic rechargeable battery according to any one of claims 8 to 14 chosen from a bulk battery and a thin film micro-battery. Utilisation d’une batterie rechargeable inorganique solide selon l’une quelconque des revendications 8 à 15 caractérisée en ce que les opérations de charge et de décharge s’effectuent à une température comprise entre - 20°C et 100°C, de préférence entre 10°C et 40°C, de façon particulièrement préférée entre 15°C et 25°C.Use of a solid inorganic rechargeable battery according to any one of Claims 8 to 15, characterized in that the charging and discharging operations are carried out at a temperature of between -20°C and 100°C, preferably between 10 °C and 40°C, particularly preferably between 15°C and 25°C. Véhicule comportant une batterie rechargeable inorganique solide massive selon l’une quelconque des revendications 8 à 15 configurée pour stocker et alimenter ledit véhicule en énergie.A vehicle comprising a bulk solid inorganic rechargeable battery according to any one of claims 8 to 15 configured to store and supply said vehicle with energy. Appareil électronique autonome de type objet connecté comportant une batterie rechargeable inorganique solide massive ou une microbatterie selon l’une quelconque des revendications 8 à 15 configurée pour stocker et alimenter ledit appareil en énergie.Autonomous electronic device of the connected object type comprising a massive solid inorganic rechargeable battery or a microbattery according to any one of claims 8 to 15 configured to store and supply said device with energy. Réseau intelligent d’électricité de type Smart Grid comportant une batterie rechargeable inorganique solide massive selon l’une quelconque des revendications 8 à 15 configurée pour stocker et alimenter ledit réseau en énergie.Smart Grid type intelligent electricity network comprising a massive solid inorganic rechargeable battery according to any one of claims 8 to 15 configured to store and supply said network with energy.
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