WO2014191931A2

WO2014191931A2 - Product of phosphorus, and of iron and/or manganese

Info

Publication number: WO2014191931A2
Application number: PCT/IB2014/061777
Authority: WO
Inventors: Arnaud APHECEIXBORDE; Yves Boussant-Roux; Claude Jacquot; Sylvain Petigny
Original assignee: Saint-Gobain Centre De Recherches Et D'etudes Europeen
Priority date: 2013-05-31
Filing date: 2014-05-28
Publication date: 2014-12-04
Also published as: WO2014191931A3

Abstract

The present invention concerns a product having a loss on ignition at 1000°C of less than 25%, and, after loss on ignition, a chemical analysis such that, in mass percentages and for a total of 100%: - 17.0% < P < 27.0%, Fe + Mn such that the molar ratio (Fe + Mn)/P is 0.4 < (Fe + Mn)/P < 1.4, elements other than P, Fe, Mn, H and O < 5.0%, H ÷ O: make up the remainder to 100%), the product comprising a phase, referred to as "PO", other than strengite or a metastrengite, said phase comprising oxygen and phosphorus elements and the iron element or the manganese element, and a crystallised phase (which can be phase PO, or not) chosen from group G_O consisting of the crystallised phases of iron oxides, the crystallised phases of manganese oxides, the crystallised phases of mixed iron and manganese oxides, or from group GP consisting of the crystallised phases of iron phosphates, the crystallised phases of manganese phosphates, the crystallised phases of mixed iron and manganese phosphates, or from group GH consisting of the crystallised phases of iron hydroxides and the crystallised phases of manganese hydroxides, said product being such that, after optional crushing into the form of particles, more than 30% by number of the particles that have a size of between 106 µm and 250 µm are heterogeneous particles, a heterogeneous particles being a particle comprising, in the cross section of the particle, first and second regions having first and second contents of a same element, ΤΊ and T2 respectively, such that ratio Tf/T2 is greater than 1.3, the element being Fe or Mn or P, the first and second regions each having a surface area greater than 1 µm2.

Description

Product of phosphorus, and iron and / or manganese

Technical area

The invention relates to a product based on phosphorus on the one hand and iron and / or manganese on the other hand, or "PFM product", and a method of manufacturing such a product. This product can especially be used as a raw material for the manufacture of a material rich in phase (s) of formula (U ₁ -a A _a ) i _{+ x} (G _b _{b b} ) _y [( _X O ₄ ). _d D _d] _z E _e, wherein:

• Li is the lithium element,

A is a lithium substituent chosen from the elements Na, K, H and their mixtures, a being less than or equal to 0.2 (substitution ratio less than or equal to 20 atomic%),

G is selected from Fe, Mn, Ni, Co, V and their mixtures,

J is a substituent of G selected from Nb, Y, Mg, B, Ti, Cu, Cr and mixtures thereof, b being less than or equal to 0.5 (substitution ratio less than or equal to 50 atomic%),

X0 ₄ is an oxoanion in which O denotes the oxygen element and X is chosen from P, S, V, Si, Nb, Mo, Al and their mixtures,

"D is chosen from F ^" anions, OH ^" , Ci ^" and their mixtures, d being less than or equal to 0.35 (substitution ratio less than or equal to 35 at%), d being zero,

E is chosen from the element F, the element Ci, the element O, the group OH, and their mixtures,

• 0 e <2,

• -0,2≤x <2,

"0.9 <y <2,

• 1 <z <3.

For the sake of clarity, these phases are called "LAGJXODE phases".

The invention also relates to a process for manufacturing such a material rich in LAGJXODE phase (s) from a feedstock comprising said PFM product.

State of the art

Lithium-ion batteries, manufactured in large quantities, can incorporate materials rich in LAGJXODE phases, especially for the manufacture of their cathode materials. Their performances as well as their lifetimes depend on, among other things, the LAGJXODE phase richness of the material used. In this application to lithium-ion batteries, the manufacture of phase-rich materials LAGJXODE comprises a step of insertion of an element, for example lithium and / or iron, into a metastrengite II phase skeleton. , FeP0 ₄ .2H ₂ 0, having a monoclinic crystalline structure, in particular by solid phase fterylation or by soft chemistry. This type of process, however, leads to high costs.

The Applicant has recently discovered that a fusion process makes it possible, surprisingly, also to manufacture a very rich melting material in the LAGJXODE phase suitable for the manufacture of lithium-ion batteries. This discovery was the subject of patent application PCT / IB2012 / 053634.

An object of the invention is to provide new raw materials suitable for the manufacture of a molten material rich phase LAGJXODE for the manufacture of lithium-ion batteries. In particular, these raw materials must present a good compromise between their workability, their cost, their potential danger and their compatibility with the manufacturing process of the very rich molten material in the LAGJXODE phase.

WO2008 / 067677 describes the use of a UFePO ₄ precursor, such as the metastrengite II phase, in the form of a crystal lattice having a suitable structure and porosity.

Summary of the invention

The invention relates to a product having a loss on ignition at 1000 ° C of less than 25%, and, after loss on ignition, a chemical analysis such that, in percentages by weight and for a total of 100%:

- 17.0% <P <27.0%,

Fe + Mn such that the molar ratio (Fe + Mn) / P is such that 0.4 <(Fe + n) / P <1.4 (and thus 18.8% <Fe + Mn <45.2% )

- other elements than P, Fe, Mn, H and O <5.0%,

- H + O: 100% complement,

the product comprising

a phase, called "PO", other than strengite (phase FePO ₄ .2H ₂ O crystallized in the orthorhombic structure) or metastrengite, said phase comprising elements oxygen and phosphorus on the one hand and the element iron and / or the manganese element on the other hand, and

a crystallized phase (which may be the PO phase or not) and chosen: in the group GB consisting of the crystallized phases of iron oxides, the crystallized phases of manganese oxides, the crystallized phases of mixed oxides of iron and of manganese, or

in the group G _P constituted by the crystallized phases of iron phosphates, the crystallized phases of manganese phosphates, the crystallized phases of mixed phosphates of iron and manganese, or

in the group G _H constituted by the crystallized phases of iron hydroxides and the crystalline phases of manganese hydroxides.

The PO phase can be crystallized or not.

When the PO phase is a said crystallized phase, the product comprises a PO phase and a said crystallized phase which are combined.

The crystalline phases of iron oxides are preferably Fe ₂ O ₃ and / or Fe ₃ O ₄ .

The crystalline phases of manganese oxides are preferably MnO and / or M ₂ 0 ₃ and / or MnO ₂ and / or n ₃ O ₄ .

Preferably a product according to the invention is heterogeneous, that is to say such that, after optional grinding to obtain particles which have a size between 106 pm and 250 pm (grinding being necessary only if it is not possible to obtain such particles without grinding), more than 30% by number of particles having a size of between 106 μm and 250 μm are heterogeneous particles, a heterogeneous particle being a particle comprising, in a section of the particle, first and second regions having first and second contents in the same element, Τ _Ί and T ₂ respectively, such that the ratio Ti / T ₂ is greater than 1, 3, the element being Fe or Mn or P, the first and second regions each having an area greater than 1 pm ² . In other words, in its particle size range between 106 μm and 250 μm, more than 30% by number of the particles are heterogeneous.

This characteristic makes it possible in particular to distinguish a product according to the invention from the products obtained by melting which, consequently, are particularly homogeneous, such as those described in EP 2 546 194 or WO 2013/011452. The same is true of hydrothermally produced products, which are characterized by very high homogeneity. The articles "Hydrothermal Synthesis and Structure of the Solid Solution (Feo-Mrto _, P0 ₄ ) -2H ₂ O", by N. Belfguira et al., Chem Crystallogr., (201 1); (oxy) hosphates and vanadium oxides for lithium batteries ", by M. Whittingham et al, J. Mater Chem, 2005, 15, 3362-3379, or "Structure of MnP0 ₄ .H ₂ 0 by Sync Rotron X-Ray Powder Diffraction", by P. Ughtfoot et al., Inorg. Chem. 1987, 26, 3544-3547 illustrate the manufacture of products by hydrothermal route.

Preferably, the ratio T fT ₂ is greater than 1.3 for more than one of the elements Fe, Mn and P. For example, a particle may be heterogeneous by the presence of an inclusion of Fe and / or an inclusion of Mn. A particle may also be heterogeneous by the presence of a concentration gradient in one of said elements, provided that the content in the most concentrated region is more than 1.3 times greater than the content in the least concentrated region.

Preferably the first and second regions each have an area greater than 2 μιη ^2, preferably greater than 3 pm ^2, preferably greater than 4 pm ² _t of preferably greater than 5 pm ^_2.

A heterogeneous product may in particular be manufactured according to a method according to the invention described below.

As will be seen in more detail in the following description, such a product, hereinafter "product according to the invention", makes it possible to manufacture, reliably, in particular according to the method described in PCT / IB2012 / 053634, a LAGJXODE phase-rich material suitable for the manufacture of lithium-ion batteries. In addition, this product does not contain a hazardous product, such as phosphoric acid and can be manufactured in industrial quantities, at a reduced cost. Finally, it is easily manipulated.

Preferably, a product according to the invention also comprises one or more of the following optional characteristics:

- The mass content of element P is greater than 18%, preferably greater than 19%, or even greater than 20% and / or less than 23%, preferably less than 22%, or even less than 21%.

The total mass content of elements Fe and Mn, Fe + Mn, is greater than 25%, preferably greater than 30%, preferably greater than 32%, preferably greater than 34%, preferably greater than 36%, and or less than 42%, preferably less than 40%, preferably less than 38%.

- The mass content of Fe element is greater than 3.7%, preferably greater than 5.6%, preferably greater than 6.7%. The molar ratio (Fe + n) / P is greater than 0.5, preferably greater than 0.6, preferably greater than 0.8, preferably greater than 0.9, and / or less than 1, 2 preferably less than 1.1. Preferably, the molar ratio (Fe + Mn) / P is substantially equal to 1.

In one embodiment, the molar ratio Mn / Fe is greater than 2.3, preferably greater than 3, preferably greater than 3.5 and less than 9, preferably less than 7, preferably less than 5, 7, preferably less than 4.5.

In one embodiment, the molar ratio Mn / Fe is greater than 0.6, preferably greater than 0.8, preferably greater than 0.9 and less than 1.5, preferably less than 1.2, preferably less than 1.1.

- 32.8% <H + O <53.2%.

H <5.0%, preferably H <3.0%, preferably H <1.0%.

The sum of the contents of other elements than P, Fe, Mn, H and O is less than 4.0%, preferably less than 3.0%, or even less than 2.0%, or even less than 1.0%; or even less than 0.5%.

- The loss on ignition is less than 20%, preferably less than 15%, preferably less than 10%, and / or greater than 1%, or even greater than 2%, or even greater than 5%.

- After loss on ignition, the oxides and phosphates represent more than 80%, more than 85%, more than 90%, more than 95%, or even substantially 100% of the mass of the product.

The crystallized phase (which may be the PO phase or not) is preferably chosen from the Go group and / or from the group G _H and / or from the group constituted by the crystallized phases of manganese phosphates and the crystallized phases of mixed phosphates of iron and manganese.

- The mass content of Fe element is greater than 3.7%, preferably greater than 5.6%, preferably greater than 6.7% and the crystallized phase (which may be the PO phase or not) is preferably chosen in the group G ₀ and / or in the group G _H and / or in the group consisting of the crystallized phases of manganese phosphates and the crystallized phases of mixed phosphates of iron and manganese.

The crystallized phases of iron phosphates, manganese phosphates, mixed iron phosphates and manganese are preferably FePO ₄ , MnPO ₄ , MnPO ₂ .nH ₂ O, "n" being an integer greater than 0, Fe ₃ H ₉ (PO) ₆ .6H ₂ O, FeH ₃ P ₂ O _e .H ₂ O, Fe ₃ H ₅ P ₈ O ₃₂ .4H ₇ O and mixtures thereof, preferably FePO ₄ , nPO ₄ , MnPO ₄ H 0 _2, Fe ₃ H ₉ (P0 ₄₎ ₆ .6H ₂ 0, FeH ₃ P ₂ 0 ₆ .H ₂ 0, Fe ₃ P ₈ H ₁₅ 0 ₃₂ .4H ₂ 0, and mixtures thereof.

- The product has a combination a phase chosen from the group G ₀ or the group G _H or from the group consisting of the crystallized phases of manganese phosphates and the crystallized phases of mixed phosphates of iron and manganese on the one hand, and

a phase chosen from the group consisting of the crystallized phases of iron phosphates on the other hand.

Preferably, said combination is chosen from combinations of a phase chosen from Fe ₂ O ₃ and / or Fe ₃ O ₄ and / or MnO and / or Mn ₂ O ₃ and / or MnO ₂ and / or Mn ₃ 0 ₄ and / or Fe (OH) ₂ , FeO (OH), Fe (OH) ₃ , Mn (OH) ₂ and / or MnPO ₄ , and / or MnPO ₄ .nH ₂ O, where "n" is a higher integer at 0 on the one hand, and a phase selected from FePO ₄ , and / or Fe ₃ H 9 (PO ₄ ) ₆ .6H ₂ O, and / or FeH ₃ P ₂ O ₈ , H ₂ O, and / or Fe ₃ H _{15 8} O ₃₂ , 4H ₂ O on the other hand.

The crystallized phases of iron hydroxides and the crystalline phases of manganese hydroxides are preferably selected from the group formed by Fe (OH) ₂ , FeO (OH), Fe (OH) ₃ , Mn (OH) ₂ .

- The strengite phase rate is less than 80%, preferably less than 70%, preferably less than 60%, preferably less than 50%, preferably less than 40%, preferably less than 30%, preferably less than at 20%, or even less than 10%, or even less than 5%. In one embodiment, the product contains substantially no strengite phase.

- The metastrengite phase rate is less than 80%, preferably less than 70%, preferably less than 60%, preferably less than 50%, preferably less than 40%, preferably less than 30%, preferably less than at 20%, or even less than 10%, or even less than 5%. In one embodiment, the product contains substantially no metastrengite phase.

The sum of the strengite and metastrengite phase levels is less than 80%, preferably less than 70%, preferably less than 60%, preferably less than 50%, preferably less than 40%, preferably less than 30%; preferably less than 20%, even less than 10%, or even less than 5%. In one embodiment, the product contains substantially no strengite and metastrengite phases.

In one embodiment, the sum of the rates of all the PO phases, indeed of all the crystallized phases other than the strengite and metastrengite phases, is greater than 10%, even greater than 20%, or even greater than 30%, or even greater than 50%, even greater than 60%, even greater than 70%, even greater than 80%, even greater than 90%, or even greater than 95%.

In one embodiment, the sum of the rates of all the PO phases, or even the rates of all the crystallized phases other than the strengite and metastrengite phases, and chosen in the groups Go, G _P and G _H is greater than 10%, even greater than 15%, even greater than 20%, even greater than 30%, even greater than 50%, even greater than 60%, or even greater than 70%, even greater than 80%, even greater than 90%, or even greater than 95%.

In one embodiment, the sum of the rates of all the PO phases, or even the rates of all the crystallized phases other than the strengite phases _. and metastrengite and selected in group G ₀ is greater than 10%, even greater than 20%, even greater than 30%, even greater than 50%, even greater than 60%, even greater than 70%, or even greater at 80% or even greater than 90%.

In one embodiment, the sum of the rates of all the PO phases, or even the rates of all the crystallized phases other than the strengite and metastrengite phases and chosen in the G _P group, is greater than 10% or greater. at 20%, your higher than 30%, even greater than 50%, even greater than 60%, even greater than 70%, even greater than 80%, or even greater than 90%.

In one embodiment, the sum of the levels of all the PO phases, or even the rates of all the crystallized phases other than its strengite and metastrengite phases and chosen in the G _H group, is greater than 10% or greater. at 20%, even greater than 30%, even greater than 50%, even greater than 60%, even greater than 70%, even greater than 80%, or even greater than 90%.

The crystallized phase is chosen:

if the molar ratio (Fe + n) / P is greater than or equal to 0.8;

in the group Go consisting of the crystallized phases of iron oxides, the crystallized phases of manganese oxides, the crystallized phases of mixed oxides of iron and of manganese, or

in the group G _H constituted by the crystallized phases of iron hydroxides and the crystallized phases of manganese hydroxides, or

in the group consisting of the crystallized phases of manganese phosphates and the crystallized phases of mixed phosphates of manganese and iron,

if the molar ratio (Fe + Mn) / P is such that 0.4 <(Fe + n) / P <0.8:

in the group G ₀ constituted by the crystallized phases of iron oxides, the crystallized phases of manganese oxides, crystallized phases of mixed oxides of iron and of manganese, or S in the group Gp constituted by the crystallized phases of iron phosphates, the crystallized phases of manganese phosphates, the crystallized phases of mixed iron and manganese phosphates, or

in the group G _H constituted by the crystallized phases of iron hydroxides and the crystallized phases of manganese hydroxides.

In one embodiment, the sum of the levels of all the crystalline phases of iron oxides, of all the crystalline phases of manganese oxides and of all the crystalline phases of mixed oxides of iron and manganese is greater than 10%, even greater than 20%, even greater than 30%, even greater than 50%, even greater than 60%, even greater than 70%, even greater than 80%, even greater than 90%, or even greater than 95% .

In one embodiment, the sum of the rates of all the crystalline phases of phosphates of the G _P group is greater than 10%, even greater than 20%, or even greater than 30%, or even greater than 50%, or even greater than 60%, even greater than 70%, even greater than 80%, or even greater than 90%.

In one embodiment, the sum of the levels of all the crystallized phases of hydroxide (s) of the group G _H is greater than 10%, even greater than 20%, or even greater than 30%, or even greater than 50%, even greater than 60%, even greater than 70%, even greater than 80%, or even greater than 90%.

The product comprises metastrengite and a crystalline phase other than metastrengite and preferably selected from the group G ₀ , preferably a crystalline phase of an iron oxide or a crystalline phase of manganese oxide.

- In one embodiment, the product is such that the fraction of particles having a size of between 106 μm and 250 μm, obtained after grinding and / or sieving the product (s), comprises more than 40%, preferably more than 50%, preferably more than 60%, preferably more than 70%, preferably more than 80%, or even more than 90%, in number of heterogeneous particles which have a ratio J 2 U ₂ preferably greater than 1 , 4, preferably greater than 1, 5, preferably greater than 1, 7, preferably greater than 2, preferably greater than 3, preferably greater than 5, preferably greater than 7, preferably greater than 10, preferably greater than 15, preferably greater than 20, preferably greater than 25, preferably greater than 30, preferably greater than 40, preferably greater than 50, even greater than 60, or even greater than 100.

- In one embodiment, the product is such that the fraction of particles having a size between 106 μιτι and 250 μm, obtained after grinding and / or sieving (s) of the product, comprises more than 40%, preferably more than 50%, preferably more than 60%, preferably more than 70%, preferably more than 80%, or even more than 90%, by number of heterogeneous particles which have a T _f / T ₂ ratio of less than 200, preferably less than 100, preferably less than 70, preferably less than 60.

The fraction of the particles having a size of between 106 μm and 250 μm, obtained after grinding and / or sieving (if any) of the product, comprises more than 30%, preferably more than 40%, or even more than 50%, more than 60% or even more than 70% or more than 80%, in number of particles of which one of said regions is an inclusion, an inclusion being a region having an area of between 5 and 150 pm ² and constituted, for more than 50% by weight of the same element chosen from Fe, Mn and P.

- An inclusion may in particular comprise more than 50% by weight of iron or manganese.

In one embodiment, a sectional view of a heterogeneous particle having a size of between 106 and 250 μm has more than 50, preferably more than 60, preferably more than 70, preferably more than 90, more preferably 150 or more than 200 inclusions per mm ² .

In one embodiment, the product is in the form of a particle, a particle powder or a block.

In one embodiment, the product is in the form of an agglomerate of particles, preferably a block, the smallest dimension of which is preferably greater than 3 mm, preferably greater than 5 mm, or even greater than 10 mm. mm and / or the largest dimension is less than 200 mm, or even less than 100 mm, or even less than 50 mm, or even less than 20 mm. Preferably, the agglomerate is an assembly of solid particles bound by means of a binder phase obtained by reacting phosphoric acid with iron oxide and / or iron hydroxide and / or oxide. of manganese and / or manganese hydroxide. In a preferred embodiment, the product is in the form of a powder of such agglomerates. The amount of binder phase in the agglomerate may be variable. In one embodiment, it may be greater than 70%, greater than 80%, greater than 90%, greater than 95%, or even substantially 100% of the mass of said agglomerate.

In one embodiment, the product is not a melted product, nor a sintered product.

In one embodiment, the product is not obtained by a process comprising a heating step leading to melting, in particular at a temperature greater than 800 ° C., and / or comprising an application of a pressure greater than 1, 5 bar or greater than 2 bar, or greater than 3 bar, or greater than 5 bar, in particular with a hydrothermal treatment. All of the optional features above may be applied to the particular embodiments below in so far as they are not incompatible with them.

In a preferred embodiment, called "FeP mode", the product according to the invention has a loss on ignition at 1000 ° C. of less than 25%, and, after loss on ignition, a chemical analysis such that, in percentages by weight and for a total of 100%:

- 17.0% <P <22.0%,

- Mn <2.0%,

Fe such that the molar ratio (Fe + Mn) / P is such that 0.9 <(Fe + n) / P <1.1, preferably such that (Fe + Mn) / P is substantially equal to 1,

- other elements than P, Fe, Mn, H and O <5.0%,

- H + O: 100% complement,

said product comprising a crystallized phase (which may be the PO phase or not), other than the strengite and metastrengite phases and selected from the group G ₀ Fe formed by the crystallized phases of iron oxides, or selected from group G _PFe constituted by the crystallized phases of iron phosphates or selected from the group G _H Fe consisting of crystallized phases of iron hydroxides.

In this embodiment, a product according to the invention also comprises one or more of the following optional features:

- The loss on ignition is less than 20%, preferably less than 15%, preferably less than 10%, and / or greater than 1%, or even greater than 5%.

- The mass content of element P is greater than 18.0%, preferably greater than 19.0% and / or less than 21.0%.

- The mass content of Fe element is greater than 34.0% and / or less than 40.0%.

- The mass content Mn element is less than 1, 0%, or substantially zero.

36.0% <H + O <45.0%.

H <5.0%, preferably H <3.0%, preferably H <1.0%.

- The crystallized phase (which may be the PO phase or not), other than the strengite and metastrengite phases, is chosen from the group G ₀ Fe constituted by the crystallized phases of iron oxides or in the group G _H pe constituted by crystallized phases of iron hydroxides. Preferably, said crystallized phase is selected from the group G ₀ Fe consisting of the crystallized phases of iron oxides, preferably Fe ₂ O ₃ and / or Fe ₃ O. Preferably, said crystallized phase is Fe ₂ O ₃ iron oxide.

In a preferred embodiment, called "MnP mode", the product according to the invention has a loss on ignition at 1000 ° C. of less than 25%, and, after loss on ignition, a chemical analysis such that, in percentages by mass and for a total of 100%:

- 17.0% <P <22.0%,

Fe <2.0%,

Mn such that the molar ratio (Fe + Mn) / P is such that 0.9 <(Fe + Mn) / P <1.1, preferably such that (Fe + Mn) / P is substantially equal to 1,

- H + O: 100% complement,

- other elements than P, Fe, Mn, H and O <5.0%,

said product comprising a crystallized phase (which may be the PO phase or not), other than the strengite and metastrengite phases and selected from the group G ₀ Mn constituted by the crystallized phases of manganese oxides, or chosen from the group G _PM n constituted by the crystallized phases of manganese phosphates or selected from the group G _H Mn consisting of crystallized manganese hydroxides.

- The mass content Mn element is greater than 34.0% and / or 40.0%, preferably less than 39.0%.

The mass content of Fe element is less than 1.0%, or even substantially zero.

36.0% <H + O <45.0%.

H <5.0%, preferably H <3.0%, preferably H <1.0%.

The sum of the contents of other elements than P, Fe, Mn, H and O is less than 4.0%, preferably less than 3.0%, or even less than 2.0%, or even less than 1.0%; or even less than 0.5%. The crystallized phase (which may be the PO phase or not) other than the strengite and metastrengite phases is chosen from the group G ₀ n constituted by the crystallized phases of manganese oxides or in the group G _P M _n constituted by the phases crystallized manganese phosphates. Preferably, said crystallized phase is MnPO ₄ .nH ₂ 0, "n" being an integer greater than 0, preferably MnPO ₄ .H ₂ 0.

In a preferred embodiment, referred to as "FeP 1 mode", the product according to the invention has a loss on ignition at 1000 ° C. of less than 25%, and, after loss on ignition, a chemical analysis such that, in percentages by weight and for a total of 100%:

- 17.0% <P <22.0%,

- (Fe + Mn) such that the molar ratio (Fe + Mn) / P is such that 0.9 <(Fe + n) / P <1.1, preferably such that (Fe + Mn) / P is substantially equal to 1, with the molar ratio Mn / Fe such that 2.3 <Mn / Fe <9,

- other elements than P, Fe, Mn, H and O <5.0%,

H + O: 100% complement,

said product comprising a crystallized phase (which may be the PO phase or not) other than the strengite and metastrengite phases and selected from the G ₀ group or the G = group or the G _H group.

The mass content of Fe element is greater than 3.7%, preferably greater than 5.6%, preferably greater than 6.7% and / or less than 11.2%, preferably less than 9.3%; preferably less than 8.2%.

- The mass content of Mn element is greater than 25.6%, preferably greater than 27.4%, preferably greater than 28.5% and / or less than 33.0%, preferably less than 31, 1% preferably less than 30.0%.

the molar ratio Mn / Fe is greater than 3, preferably greater than 3.5 and / or less than 5.7, preferably less than 4.5.

40.0% <H + O <48.0%.

H <5.0%, preferably H <3.0%, preferably H <1.0%. The crystallized phase (which may be the PO phase or not) other than the strengite and metastrengite phases is preferably chosen from the group G _P , preferably a manganese phosphate or a mixed manganese and iron phosphate, preferably a manganese phosphate, preferably MnPO ₄ .nH ₂ 0, "n" being an integer greater than 0, preferably MnPO ₄ .H ₂ 0.

In a preferred embodiment, called "MFeP mode 2", occurs according to the invention has a loss on ignition at 1000 ° C less than 25%, and, after loss on ignition, a chemical analysis such that, in percentages by weight and for an iota! 100%:

- 1 7.0% <P <22.0%,

- (Fe + Mn) such that the molar ratio (Fe + Mn) / P is such that 0.9 <(Fe + n) / P <1.1, preferably such that (Fe + n) / P is substantially equal to 1, with the molar ratio Mn / Fe such that 0.6 <Mn / Fe <1.5,

- other elements than P, Fe, Mn, H and O <5.0%,

- H + O: complement to 00%,

said product having a crystallized phase (which may be the PO phase or not), other than the strengite and metastrengite phases and selected from the G ₀ group or the G _P group or the G _H group.

The mass content of Fe element is greater than 14.9%, preferably greater than 16.7%, preferably greater than 17.4% and / or less than 23.0%, preferably less than 20.4%; preferably less than 19.7%.

The mass content of element Mn is greater than 13.9%, preferably greater than 16.4%, preferably greater than 17.2% and / or less than 21.9%, preferably less than 20.1%; preferably less than 19.4%.

The molar ratio Mn / Fe is greater than 0.8, preferably greater than 0.9 and / or less than 1.2, preferably less than 1.1.

40.0% <H + O <48.0%.

H <5.0%, preferably H <3.0%, preferably H <1.0%. The crystallized phase (which may be the PO phase or not) other than the strengite and metastrengite phases is preferably chosen from the group G _P , preferably a manganese phosphate or a mixed manganese and iron phosphate, preferably a manganese phosphate, preferably nP0 ₄ .nH ₂ 0, where "n" is an integer greater than 0, preferably MnPO ₄ .H ₂ 0.

The invention also relates to a method of manufacturing a product according to the invention, said method comprising the following steps:

a) mixing a feedstock comprising:

- (particles into an oxide and / or an iron hydroxide and / or

particles in an oxide and / or a hydroxide of manganese), and

a solution of phosphoric acid H ₃ PO _{4 having a} mass concentration of H ₃ PO ₃ greater than 60%, in an amount such that the molar ratio (Fe + n) / P is between 0.4 and 1, 4,

the set of said particles having a median diameter D _{50 of} less than 100 μm, b) shaping and drying so as to obtain a product in the form of particles or of a block, preferably in the form of a block,

c) optionally crushing and / or grinding and / or grinding,

d) optionally granulometric selection,

the composition of the feedstock and drying being determined so that the particles or the block obtained at the end of step b) is a product according to the invention.

In particular, the drying is sufficiently advanced that the loss on ignition in the product obtained is reduced.

The invention also relates to a process for manufacturing a molten material comprising a step of melting a feedstock comprising a product according to the invention.

The invention relates in particular to a method comprising the following steps:

A) preparation of a feedstock comprising a product having a loss on ignition at 1000 ° C of less than 25% and, after loss on ignition, a chemical analysis such that, in percentages by weight and for a total of 100%:

- 17.0% <P <27.0%,

Fe + Mn such that the molar ratio (Fe + Mn) / P is such that 0.4 <(Fe + Mn) / P <1, 4,

- other elements than P, Fe, Mn, H and O <5.0%,

- H + O: complement to 00%, the product comprising a phase, called "PO", other than strengite or metastrengite, said phase comprising oxygen and phosphorus elements on the one hand and the iron element and / or the manganese element on the other hand, and a crystalline phase preferably chosen:

if the molar ratio (Fe + Mn) / P is greater than or equal to 0.8:

in the group G ₀ constituted by the crystallized phases of iron oxides, the crystallized phases of manganese oxides, the crystallized phases of mixed oxides of iron and of manganese, or

if the molar ratio (Fe + Mn) / P is such that 0.4 <(Fe + Mn) / P <0.8:

in group G ₀ consisting of the crystallized phases of iron oxides, the crystallized phases of manganese oxides, the crystallized phases of mixed oxides of iron and manganese, or

in the group G _P constituted by the crystallized phases of iron phosphates, the crystallized phases of manganese phosphates, the crystallized phases of mixed iron and manganese phosphates, or

in the group G _H constituted by the crystallized phases of iron hydroxides and the crystalline phases of manganese hydroxides,

B) melting said starting charge so as to obtain a liquid mass, for example in the form of a droplet;

C) solidification of said liquid mass so as to obtain a molten material.

Preferably, the product used is a product according to the invention, which may in particular have one or more of the optional characteristics described above.

Preferably, the starting charge is determined in order to obtain a molten material comprising at least one crystalline phase of formula (Li ₁ _, aA _a ) _{+ x} (G ₁ -b _b ) _y [(XO ₄ ) _{1 -d} D _d ] _z Ee, or "LAGJXODE phase", in which:

Li is the lithium element,

A is a lithium substituent chosen from the elements Na, K, H and their mixtures, a being less than or equal to 0.2, G is chosen from the elements Fe, n, Ni, Co, V and their mixtures,

- J is a substituent of G selected from Nb, Y, Mg, B, Ti, Cu, Cr and mixtures thereof, b being less than or equal to 0.5,

X0 is an oxoanion in which O denotes the oxygen element and X is chosen from the elements P, S, V, Si, Nb, Mo and their mixtures,

- D is chosen from F ^" , OH ^" , Ci ^" anions and their mixtures, d being less than or equal to 0.35,

E being chosen from the element F, the element Cl, the element O, the group OH, and their mixtures,

- 0 <e≤2,

- -0.2 <x 2,

- 0.9 <y <2,

- 1≤ z <3.

The starting load is not exclusively made of product according to the invention.

All methods described in PCT / IB2012 / 053634 can be implemented.

In one embodiment, said method comprises, after step C), its following steps:

D) Optionally, crushing and / or grinding and / or granulometric selection and / or agglomeration of the molten material;

E) Preparation of a mixture comprising said melted material, optionally crushed and / or ground and / or selected granulometrically and / or agglomerated;

F) Shaping said mixture in the form of a preform;

G) Drying and / or hot rolling to obtain a cathode;

H} Integration of said cathode in a lithium-ion battery.

The invention also relates to a method for manufacturing a cathode for a lithium-ion battery comprising the manufacture of a product according to the invention, the preparation of a feedstock comprising said product according to the invention, the melting of said starting charge according to a method according to the invention, and then, preferably, the manufacture, from the obtained molten material, of a cathode.

Definitions

"Loss on ignition" at 1000 ° C conventionally determines the amount of the constituents of a product that are extracted from said product by a heat treatment at 1000 ° C. It is measured as a percentage by mass based on the product. By extension, the loss on fire also denotes said constituents. The fire loss includes in particular the water content.

The "fire" treatment to extract the loss on ignition is continued for a time sufficient for the composition of the product to be stabilized. It can be carried out for example on a powdered product, for 2 hours, under air and at atmospheric pressure.

A fire treatment is necessary to characterize a product according to the invention. Indeed, its fusion of a product according to the invention leads to the extraction of the compounds which are extracted during the fire treatment. These compounds will therefore no longer interfere with the characteristics of the molten material. To define the invention, it is therefore useful to isolate the constituents that will remain in the molten material. In addition, it is not possible to characterize the product of the invention differently, since a part of the loss on ignition can concern compounds comprising the element P. A chemical analysis before loss on ignition would therefore not characterize the invention in a completely satisfactory manner.

By "iron oxide phase (s)" and "manganese oxide (s)" are meant phases identified as such by XRD.

By "iron phosphates, manganese phosphates, mixed iron and manganese phosphates" is meant an electrically neutral compound of the formula P _x Fe _y n ₇ H ₁ O _w (OH) ₂ , nH ₂ 0, x and w being integers> 0, y, z, t, n and v being integers> 0 and y + z> 0. FeP0 ₄ is an example of iron phosphate. MNPO. and MnPO ₂ .H ₂ O are examples of manganese phosphates.

By "iron hydroxide (s)" and "manganese hydroxide (s)" is meant an electrically neutral compound of formula Fe _x O _v (OH) _y , and Mn _x <C _v (OH) _y <, respectively, with x, y, x 'and y' being integers> 0, v and v 'being integers ≥ 0. Fe (OH) ₂ and FeO (OH) are examples of iron hydroxides. Mn (OH) ₂ is an example of manganese hydroxide.

The "quantity of a LAGJXODE phase" is the percentage of said LAGJXODE phase on all the crystallized phases of the material, this assembly being called "crystallized part".

For a LAGJXODE phase considered, an International Center for Diffraction Data (ICDD) sheet is used to identify the angular domains of the diffraction peaks corresponding to said LAGJXODE. For example, ICDD record 40-1499 is that of the olivine phase LiFeP0 ₄

The amount of LAGJXODE phase can be evaluated by the following formula (1): T - 100 ^* (A _LAG jxoDE) / (A _L AGJXODE ⁺ Secondary Apnases) (1)

or

• ALAGJXODE is the area of the non-superimposed higher intensity diffraction peak or its non-superimposed higher intensity diffraction intensity, of the LAGJXODE phase, measured on an X-ray diffraction pattern of said material, for example obtained from a device of the type diffractometer D5000 BRUKER company provided with a tube DX copper. The acquisition of the diffraction pattern is carried out from this equipment, on an angular range 2Θ of between 5 ° and 80 °, with a pitch of 0.02 °, and a counting time of 1 s / step. The sample is rotating on itself in order to limit the preferential orientations. The processing of the diagram obtained can be achieved for example using the EVA software, without deconvolution treatment;

β Aph side _ase s is the sum of the areas of secondary phases, measured on the same diagram, without deconvolution processing. The area of a secondary phase is that of its diffraction peak of greater non-superimposed intensity or of its diffraction muitiplet of higher non-superimposed intensity. The secondary phases are those detectable by X-ray diffraction other than the LAGJXODE phase. Among others, Fe ₂ 0 ₃ , FePO ₄ , Li ₃ PO ₄ , AIPO ₄ or Li ₃ Fe ₂ (PO ₄ ) 3 may be secondary phases identified on the X-ray diffraction diagram, in particular when the LAGJXODE is LiFePO ₄ . A "non-superimposed" diffraction peak is a diffraction peak corresponding to a single phase (no overlap of two peaks corresponding to two different phases). Similarly, a diffraction multiplet "not superimposed" is a diffraction byte corresponding to a single phase.

The precision of such a measurement is equal to 0.3% in absolute.

The "rates" of metastrengite and strengite are the mass percentages of the metastrengite and strengite phase, respectively, over all of the crystallized phases of the product, this set being referred to as the "crystallized portion".

A product or a material is conventionally said to be "melted" when it is obtained by a process implementing a melting of raw materials until a liquid mass is obtained (which may contain solid particles, but in insufficient quantity to structure said liquid mass, so that it must be contained in a container to keep its shape), then solidification by cooling. "Particle" means a solid object whose size is less than 10 mm, preferably between 0.01 pm and 5 mm. An agglomerate of particles is an assembly of solid particles, the bonds between the particles not being ensured by a fusion, even local, of these particles. In particular, the bond may correspond to an ensured hold by reaction of phosphoric acid with iron oxide and / or iron hydroxide and / or manganese oxide and / or hydroxide. manganese. By "size" of a particle is meant the diameter of the sphere of the same volume. The particle size of a powder is classically evaluated by a particle size distribution characterization performed with a laser granulometer. The laser granulometer may be, for example, a Partica LA-950 from the company HORIBA.

Percentiles 50 (D ₅₀ ) and 99.5 (D ₉ 9, ₅ ) are the particle sizes corresponding to percentages, by mass, of 50% and 99.5%, respectively, on the particle size distribution curve. cumulative particle size of the powder, the particle sizes being ranked in ascending order. For example, 99.5% by weight of the particles of the powder are smaller than D ₉₉ . ₅ and 0.5% of the particles in mass have a size greater than D _99.5 . The percentiies can be determined ^using a particle size distribution achieved using a laser granulometer.

The term "maximum size of a powder", the 99.5 percentile (D _g g _[5) of said powder. The "50th percentile" (D ₅₀ ) of said powder is called the "median size of a powder".

By "block" is meant a solid object that is not a particle. A "solid" object is an object that retains its shape without having to be contained in a container (in the absence of other constraints than gravity).

By "impurities" is meant the inevitable constituents introduced involuntarily and necessarily with the raw materials or resulting from reactions with these constituents. Impurities are not necessary constituents, but only tolerated. For example, the compounds forming part of the group of oxides, nitrides, oxynitrides, carbides, oxycarbides, carbonitrides and metallic species of sodium and other alkalis, chromium, yttrium, magnesium, boron, copper, and niobium are impurities if their presence does not occur. is not desired.

Unless otherwise indicated, all grades are percentages by mass.

"Fe + Mn" means the sum of Fe and Mn contents.

"Containing a", "comprising a" or "containing a" means "having at least one", unless otherwise indicated. For example, a product according to the invention can have a crystallized phase selected from the group Go and a crystalline phase selected from the group G _P.

"Comprising first and second regions" means "comprising at least a pair of first and second regions".

detailed description

Product according to the invention

A product according to the invention is preferably manufactured according to steps a) to d) above. In step a), the composition of the feedstock is determined so that the block or particles obtained at the end of step b) are in a product according to the invention, and possibly for exhibit one or more of the optional features of a product according to the invention. The person skilled in the art knows how to adapt the starting load to take account of the drying conditions.

The amounts of iron oxide (s) and / or hydroxide (s), and / or oxide (s) and / or manganese hydroxide (s), and phosphoric acid are preferably such that the molar ratio (Fe + Mn) / P is greater than 0.5, preferably greater than 0.6, preferably greater than 0.8, preferably greater than 0.9 and less than 1.2, preferably less than 1.1 . Preferably, (Fe + n) / P is substantially equal to 1.

Preferably, the elements Fe and Mn are provided by oxides. Preferably, the iron oxide is selected from Fe ₂ O ₃ and Fe ₃ O ₄ . Preferably the iron oxide is Fe ₂ O ₃ . Preferably the manganese oxide is selected from MnO, Mn ₂ 0 ₃ , n _{3 0} and MnO ₂ and mixtures thereof.

In one embodiment, the feedstock does not contain manganese hydroxide.

If it contains, the manganese hydroxide is preferably n (OH) ₂ .

In one embodiment, the feedstock does not contain iron hydroxide. If it contains, the iron hydroxide is preferably selected from Fe (OH) ₂ , FeO (OH), Fe (OH) ₃ , and mixtures thereof.

The phosphoric acid mass concentration of the solution is preferably greater than 70%, preferably greater than 80% and / or less than 90%. A mass concentration substantially equal to 85% is well suited.

In one embodiment, in particular for producing a product according to the FeP mode, the amount of element Mn in the feedstock is preferably less than 2%, preferably less than 1%, or even substantially zero, in percentages by mass. the starting charge. In one embodiment, in particular for producing a product according to the MnP mode, in step a), the amount of Fe element in the feedstock is less than 2%, preferably less than 1%, or even substantially zero. in percentages by mass of the starting charge. In one embodiment, in particular for producing a product according to the MFeP 1 mode, the molar ratio Mn / Fe in the feedstock can be greater than 2.3, preferably greater than 3.0, preferably greater than 3. , 5 and preferably less than 9, preferably less than 5.7, preferably less than 4.5.

In one embodiment, in particular for producing a product according to the FeP 2 mode, the molar ratio Mn / Fe in the feedstock may be greater than 0.6, preferably greater than 0.8, preferably greater than 0. , 9 and less than, 5, preferably less than 1, 2, preferably less than 1, 1.

Whatever the embodiment considered, impurities from the raw materials may be present.

In particular, the elements Ba, Sr, Yb, Ce, Ca can be found as impurities; and Si, S, Na, K, Nb, Y, B, Ti, Cu, Cr, Mg, Al when it is not desired that the LAGJXODE phase to be manufactured from the product according to the invention contains these elements.

Preferably, the total mass content of impurities in the feedstock is less than 5.0%, preferably less than 4.0%, preferably less than 3.0%, preferably less than 2.0%, of preferably less than 1.0%, or even less than 0.7%. Preferably again,

- Ca <2.0%, preferably Ca <1.0%, preferably Ca <0.8%, preferably Ca <0.5%, preferably Ca <0.2%, preferably Ca <0, 1%, and / or

Al <2.0%, preferably Al <1.0%, preferably Al <0.8%, preferably Al <0.5%, preferably Al <0.3%, preferably <0.2 %, if X0 ₄ does not contain aluminum, and / or

- If <0.2%, preferably Si <0.15%, if X0 ₄ does not contain silicon, and / or

Na <2.0%, preferably Na <1.0%, preferably Na <0.8%, preferably Na <0.6%, preferably Na <0.5%, preferably Na <0, 4%, if A does not contain sodium, and / or

Ti <2.0%, preferably Ti <1.0%, preferably Ti <0.8%, preferably Ti <0.5%, preferably Ti <0.2%, preferably Ti <0, 1%, if G does not contain titanium.

In order to manufacture a block or a particle, preferably a block, at the end of step b), those skilled in the art know, in particular, how to choose a granulometry of the raw material powders and a concentration of suitable phosphoric acid. If necessary, he knows the rules to adapt the starting load, and in particular, he knows that to improve the behavior of the product it is possible:

in step a), to reduce the median diameter D ₅₀ , and / or in step a), to increase the mass concentration of the phosphoric acid, and / or

in step b), to increase the drying temperature, and / or

in step b), to increase the holding time at the maximum drying temperature.

The median diameter D ₅₀ is preferably less than 90 μm, preferably less than 80 μm, preferably less than 70 μm, preferably less than 60 μm, preferably less than 50 μm, preferably less than 40 μm, and preferably less than 40 μm. at 30 pm, preferably less than 20 pm, preferably less than 10 pm, preferably less than 5 pm, preferably less than 1 pm, preferably less than 0.5 pm.

The mixture is preferably carried out at a temperature below 50 ° C, preferably below 30 ° C and / or above 10 ° C, preferably above 15 ° C. A mixture made at ambient temperature is well suited.

The mixing time is adapted to obtain a homogeneous mixture. Those skilled in the art know how to adapt the mixing time according to the mixing equipment used.

Preferably, there is no intermediate step between steps a) and b). In particular, preferably, the mixture resulting from step a) does not undergo hydrothermal treatment.

In step b), the drying temperature is preferably greater than 80 ° C, preferably greater than 100 ° C, or even greater than 200 ° C, or even greater than 300 ° C and / or less than 450 ° C, preferably below 400 ° C.

The drying time is less than 24 hours, preferably less than 15 hours. Advantageously, the phenomena of segregation are limited or even eliminated. The person skilled in the art knows how to adapt the drying conditions and the shape of the product to be dried, in particular its thickness, so as to eliminate a specific quantity of water.

Preferably, the starting charge is determined so that at the end of step b), the product according to the invention is such that the sum of the levels of all the PO phases, or even the rates of all the crystallized phases. other than the strengite and metastrengite phases and chosen in groups Go, G _P and G _H , is greater than 10%, even greater than 20%, even greater than 30%, or even greater than 50%, or even greater than 60%, even greater than 70%, even greater than 80%, even greater than 90%, or even greater than 95%.

The reaction with phosphoric acid advantageously leads to agglomeration of the particles, which makes them easier to handle.

In one embodiment, steps a) and b) are merged. For example, the mixture may be carried out in a heating mixer, or raw materials of the feedstock. may be reheated before being introduced into the feedstock. This embodiment is however not preferred.

To manufacture a product according to the FeP mode, the method is preferably such that:

in step a), the feedstock comprises particles of an oxide and / or an iron hydroxide, the molar ratio (Fe + Mn) / P in the feedstock being between 0.9 and 1, 1, preferably substantially equal to 1, wherein the median diameter D ₅₀ is less than 10 μm, preferably less than 1 μm, preferably less than 0.5 μm, and the mass concentration of phosphoric acid H ₃ PO ₄ being greater than 80%, and

in step b), the drying is carried out at a temperature of between 90 ° C. and 120 ° C., preferably during a holding time at this temperature of between 8 hours and 15 hours.

To manufacture a product according to the nP mode, the method is preferably such that:

in step a), the feedstock comprises particles of raw materials made of an oxide and / or a manganese hydroxide, the molar ratio (Fe + Mn) / P in the feedstock being between 0.9 and 1, 1, preferably substantially equal to 1, the median diameter D ₅₀ of the raw material particles being less than 60 μm, preferably less than 50 μm, preferably less than 10 μm, preferably less than 1 μm, of preferably less than 0.5 μm, and the mass concentration of phosphoric acid H ₃ PO ₄ being greater than 80%, and

in step b), the drying is carried out at a temperature of between 90.degree. C. and 120.degree. preferably during a holding time at this temperature between 8 hours and 15 hours.

To manufacture a product according to the MFeP 1 mode, the method is preferably such that:

in step a), the starting load comprises

particles in an oxide and / or an iron hydroxide,

particles in an oxide and / or manganese hydroxide,

the molar ratio (Fe + Mn) / P in the feedstock being between 0.9 and 1, preferably substantially equal to 1, with the molar ratio Mn / Fe in the feedstock greater than 2.3, preferably greater than 3.0, preferably greater than 3.5 and less than 9.0, preferably less than 5.7, preferably less than 4.5, the median diameter of the raw material particles being less than 60 pm, preferably less than 50 pm, preferably less than 10 pm, preferably less than 1 pm, preferably less than 0.5 μm, and the mass concentration of phosphoric acid H 3 PO 4 being greater than 80%, and

To manufacture a product according to the MFeP 2 mode, the method is preferably such that:

in step a), the starting load comprises

particles in an oxide and / or an iron hydroxide,

particles in an oxide and / or manganese hydroxide,

the molar ratio (Fe + Mn) / P in its feedstock being between 0.9 and 1, 1, preferably substantially equal to 1, with the molar ratio Mn / Fe in the feedstock greater than 0.6 , preferably greater than 0.8, preferably greater than 0.9 and less than 1.5, preferably less than 1.2, preferably less than 1.1, the median diameter D ₅₀ of the raw material particles being less than 60 μm, preferably less than 50 μm, preferably less than 10 μm, preferably less than 1 μιη, preferably less than 0.5 μm, and the mass concentration of phosphoric acid H ₃ PO 4 being greater than 80%, and

Those skilled in the art will know how to adapt the composition to step a) and its drying conditions in step b) to make a PO phase. In particular, he knows how to limit or even avoid the self-absorption of iron in order to create another phase than the strengite and metastrengite phases, and in particular metastrengite, in particular by adapting the pH conditions, in particular by increasing the acidity, and / or by adapting the temperature conditions, in particular by reducing the temperature, and / or by adapting the phosphoric acid concentration conditions, in particular by being in a more concentrated medium.

The reaction is mainly a surface reaction.

In step c), optional, the product according to the invention obtained at the end of step b) is swept and / or crushed and / or ground. All types of scrubbers, crushers and grinders are usable. Preferably, a jaw crushing is used. In one embodiment, the method comprises a step c).

In step d), the product according to the invention, optionally after grinding and / or grinding and / or crushing, may undergo a granulometric selection operation depending on the intended applications, for example by sieving.

When it is intended to be melted to manufacture a molten material rich in LAGJXODE phase intended for the manufacture of lithium-ion batteries, the product according to the invention is preferably in the form of a set of blocks, the smallest dimension is greater than 3 mm, preferably greater than 5 mm and the largest dimension is less than 200 mm. Preferably, during the entire manufacturing process, the temperature remains below 600 ° C., preferably below 450 ° C., and the pressure remains below 5 bar, preferably below 3 bar, preferably below 2 bar, preferably less than 1.5 bar, preferably remains atmospheric pressure.

Product according to the invention

A product according to the invention, in particular manufactured according to a process according to the invention, preferably has the shape of a block which can be handled without disintegrating.

The low loss on ignition and the phosphoric setting make it possible to obtain agglomerates, in particular blocks, which can be handled without disintegrating. The low loss on ignition also makes it possible to limit the departure of gases during the fusion and thus to better control this step. Thus, the lower the loss on ignition, the better the process of manufacturing the molten material.

In one embodiment, the loss on ignition is less than 10%, or even less than 5%. The control of the manufacturing process of the molten material is then optimal.

Achieving such low fire losses, however, requires heat treatment. Indeed, the conventional sources of phosphorus, and in particular the sources of phosphoric acid, always bring water. For example, phosphoric acid sources typically comprise about 15% water.

According to the invention, an optimal compromise between the cost and the control of the melting process is obtained with a loss on ignition greater than 1%, or even greater than 5%.

Preferably, the water content represents more than 80%, more than 90%, more than 95%, or even substantially 100% of the loss on ignition, in percentage by weight. The water content may be less than 25%, preferably less than 20%, preferably less than 15%, preferably less than 10%, or even less than 5%, less than 2%, or even substantially zero. To obtain the optimum compromise, the water content is preferably greater than 1%, or even greater than 5%. The content of "other elements" (other than P, Fe, Mn, H and O) is preferably less than 4.0%, preferably less than 3.0%, preferably less than 2.0%, or even less at 1, 0%, or even less than 0.5%.

In one embodiment, the "other elements" are impurities.

Preferably,

Na <2.0%, preferably Na <1.0%, preferably Na <0.5%, preferably Na <0.3%, or even Na <0.2% and / or

Al <2.0%, preferably Al <1.0%, preferably Ai <0.5%, or even Ai <0.3%, preferably Al <0.2%, and / or

Ti <2.0%, preferably Ti <1.0%, preferably Ti <0.5%, preferably Ti <0.3%, preferably Ti <0.2%.

Material rich in LAGJXODE phase (s)

To manufacture a material rich in LAGJXODE phases, all the processes described in PCT / IB2012 / 053634, incorporated by reference, can be implemented in particular. The raw materials and, optionally, the gaseous environment of these processes are, however, limited so that the crystallized portion of the molten material rich in LAGJXODE phases necessarily has, for more than 99.3% by mass, the same LAGJXODE phase.

In particular, such a method can be implemented in order to manufacture a molten material comprising at least one LAGJXODE phase, in which:

G is selected from the elements Fe and / or Mn, and optionally Ni, Co, V and mixtures thereof, and

X comprises P and optionally an element chosen from S, V, Si, Nb, Mo, Al and their mixtures,

and in particular a molten material having at least one crystalline phase of formula (L. _has Aa) i ₊ x (G _1. _b _PG) _y (P0 _4), preferably of formula Li _{1 + x} (G) _y (P0 ₄ ), with G selected from the elements Fe and / or Mn. In particular, said phase may be the LiFePO ₄ or LiMnPO ₄ or LiMno phase. ₈ Fec.2PO,) or LiFe _0.5 Mn _0, 5POi.

In one embodiment, the amount of said LAGJXODE phase, preferably of said phase of formula Li _{+ x} (G) _y (PO ₄ ), with G selected from the elements Fe and / or Mn, on the basis of said part crystallization of the molten material is greater than 50%, preferably greater than 70%, preferably greater than 80%, preferably greater than 90%, preferably greater than 95%, preferably greater than 99%, preferably greater than 99.5%, preferably greater than 99.7%, preferably greater than 99.8%, preferably greater than 99.9%, preferably is substantially 100%. Such a molten material obtained is particularly well suited for application as an electrode of a lithium-ion battery. To produce a material rich in LAGJXODE phases, a method comprising the following steps is suitable:

Mixture of raw materials so as to form a feedstock comprising a product according to the invention,

"Melting of the feedstock until a liquid mass is obtained,

Cooling until complete solidification of said liquid mass, so as to obtain a molten material,

Optionally, crushing and / or grinding and / or granulometric selection of said molten material,

Optionally thermal treatment of the molten material at a lower temperature than the melting temperature T _{f of} said molten material and between T _f - 800 ° C, or 500 ° C if T _f - 800 ° C is less than 500 ° C , and T _f - 50 ° C, during a hold time greater than 90 minutes, and in a reducing environment,

the raw materials in step A) and, optionally, the gaseous environment in step B), being determined so that the crystallized portion of said molten material has at least one LAGJXODE phase.

In step A), preferably, the product according to the invention is introduced into the feedstock to be melted without having undergone any other heat treatment than drying in step b).

Examples

Characterization methods

The chemical and phase determination analyzes were carried out on samples which, after grinding, had a median size of less than 40 μm.

Chemical analysis was performed by X-ray fluorescence and Inductsvely Coupled Plasma or ICP for lithium and impurities.

The heterogeneity of a product according to the invention is evaluated on the basis of measurements of the heterogeneity made on particles of size between 106 μm and 250 μm, possibly obtained after grinding and sieving of the product. The nature of the crushing and / or sieving are of no importance on the results, provided that this grinding and / or sieving makes it possible to constitute a significant fraction (for example having more than 5, more than 100, more than 1000 particles) of particles of size between 106 pm and 250 pm.

The measurement of the contents in the same element, ΤΊ and T ₂ , can easily be performed by an energy spectrometric analysis (or "EDS" in English), by means of a microprobe on a polished section of said particle. In the examples below, this method was used to search, in a section of a particle, the regions with the highest content and the lowest content of an element, then the ratio between these maximum and minimum levels was calculated. In Table 3, the same measurement was made on 5 particles of the same example. The detection of inclusions within the product in the form of a particle of size between 106 μm and 250 μm, obtained by possible grinding and sieving, can easily be carried out from cliches of said particle. taken using a scanning electron microscope. For this, particles of the product are coated with an epoxy resin and then polished to obtain a good surface finish, said polishing being carried out at least with a 1200-grade diamond abrasive disk, preferably with a diamond suspension. The polishes are then metallized with gold. Images are then made using a scanning electron microscope (SEM), preferably in a backscattered electron mode to obtain a very good contrast between the inclusions and the other phases present. In the present case, the following conditions have been applied during the production of said images on an FEI scanning electron microscope equipped with a GAD detector:

- High vac - "field-free" mode,

- Working Distance (WD): 4.0 mm,

- High Voltage (HV): 10 keV,

- Spot: 4.0,

- Diaphragm. : 50 pm,

- Magnification: x500,

- Contrast: 72.9,

- Brightness: 38.2.

Each shot has a minimum of 1024x884 pixels, without the scale bar. The magnification used is such that at least 3 particles of sizes between 106 μm and 250 μm are fully included in the image.

The image is analyzed using the image J software, available at http://rsbweb.nih.gov/ij/ according to the following 4-step method:

Step 1: Pre-treatment

- open the image in imageJ; - Convert the image, initially in RGB format, to 8-bit, using the "Image>Type>8-bit"function;

- cut the image ("Crop" function) to remove the scale bar or any other additional information on the image;

define the scaling factor of the image using the "Analysis> Set Scale" function so that the dimensions can be measured directly in microns by converting a number of pixels into a dimension expressed in microns;

Step 2: Determining the number of inclusions present in a particle

- Binarize the image with the "Image> Adjust> Threshold" function in order to extract the inclusions to be analyzed from the rest of the image (resin and the rest of the particle). The inclusions must appear in white (grayscale = 255), and the rest of the image in black (grayscale = 0);

- select the inclusions of a particle entirely contained in the image and analyze them using the function "Analysis> Analysis Particles". Select only the surface inclusions between 5 μνη ² and 150 pm ² , specifying the previously mentioned limits in the "Size" field. In the "Circularity" field keep the default values (ie between 0 and 1). Check the "Disptay results" and "Clear results" boxes to purge the result file and display the number of inclusions detected;

-Identify the number of inclusions detected in the chosen particle;

Step 3: Determining the surface of the particle

- Start from the image obtained at the end of the pretreatment;

- Binarize the image with the function "Image> Adjust> Threshold" so as to extract the particles this time from the rest of the image. These appear in white (gray level = 255), and the remainder of the image in black (gray level = 0);

- select the same particle as that used for counting inclusions (previous step);

- Analyze said particle using the function "Analysis> Analysis Particles". In the "Size" field, do not specify minimum or maximum limits. In the field "Circularity" keep the default values (ie between 0 and 1). Check the "Display results" and "Clear results" boxes to purge the result file and display the value of the surface of the particle in question;

- In the result table generated, identify the value of the surface of the chosen particle ("Area" column) expressed in pm ² ; Step 4: Calculation of the concentration of inclusions in the selected particle

Divide the number of inclusions detected (result of step 2) by its value of the surface of the particle (result of step 3).

The determination of the amount of LAGJXODE phase was carried out on the basis of the X-ray diffraction diagrams acquired with a BRUKER D5000 diffractometer provided with a copper DX tube.

Using the EVA software (marketed by BRUKER) and after performing a continuous background subtraction (background 0.8), it is possible to measure the area A _LA GJXODE (without deconvolution treatment) of the main peak or main diffraction multiplet of the LAGJXODE and, for each of the secondary phases, the area A _ps (without deconvolution treatment) of the peak of higher non-superimposed intensity or the multiplet of higher intensity not superimposed. We can then calculate the total area A secondary _phases by the sum of the areas A _ps . The phase quantity LAGJXODE is then calculated according to formula (1).

Thus, if the LAGJXODE phase is the only phase present in the X diffraction pattern, the LAGJXODE phase quantity is equal to 100%.

Metastrengite and strengite phase rates are conventionally evaluated by the metered additions method, by measuring corresponding areas of diffraction peaks.

The X-ray diffraction patterns can be obtained with a BRUKER D5000 diffractometer provided with a copper DX tube and a 0.6 mm receiving slot, over an angular range of between 5 ° and 80 °. with a step of 0.02 °, and a counting time of 2 s / step. During the measurement, the sample is preferably rotated on itself in order to limit the preferred orientations.

The International Center for Diffraction Data (ICDD) sheets 01-70-9910 and 01-70-9911, corresponding to the ICDD sheet of metastrengite II and the ICDD record of strengite, respectively, make it possible to identify peaks common to the metastrengite and strengite phases for 2Θ values of 20.4 ° and 18.2 °, a peak considered specific to the metastrengite phase for a 2Θ value of 32.2 ° and a peak specific to the strengite phase for a value 2Θ of 16.2 °. Specific peaks are however lower than common peaks. To improve the accuracy of the measurement, it is preferable to apply the method of the added additions on the common peaks centered on a 2Θ value of 20.4 ° if these peaks do not show overlap with at least one peak of another phase than the phase to be measured. Otherwise, it is best to apply its method of metered additions on common peaks centered on a value 2Θ of 18.2 ° if these peaks do not show overlap with at least one peak of another phase than the phase to be measured. Otherwise, His method of metered additions is applied to the peak specific to the phase to be measured. In case of simultaneous presence of the metastrengite and strengite phases, it is also possible to evaluate the rate of metastrengite and strengite phases by the method of additions dosed from a common peak, for example the peak centered on a 2Θ value of 20. , 4 °, not showing recovery with another phase.

An X-ray diffraction diagram of the sample to be analyzed makes it possible to identify whether the sample comprises one and / or the other of the metastrengite and strengite phases, depending on whether or not this diagram has peaks with the above-mentioned 2Θ values.

For the application of the metered addition method, four homogeneous mixtures of the sample to be analyzed are prepared with a standard sample present in the following quantities, respectively: 0.5x (C / P) xm, (C / P) xm , 1.5x (C / P) xm, and 2x (C / P) xm,

- m denoting the mass of the sample to be analyzed,

P denotes the mass percentage, in the standard sample, of the phase to be measured, and

Where C denotes the ratio of the intensity of a peak of the phase considered in the sample to be analyzed to the intensity of the corresponding peak in the standard sample.

For example, if the initial mass of the sample to be analyzed is equal to 2g, if C is equal to 0.6 (ie 60%) and if P is equal to 0.8 (ie 80%), then we add to sample to be analyzed a standard sample quantity equal to 0.5x (0.6 / 0.8) x2 is 0.75g, (0.6 / 0.8) x2 is 1.5g, 1, 5x (0 , 6 / 0.8) x2 is 2.25g, 2x (0.6 / 0.8) x2 is 3g, respectively.

P can be determined by Rietveid analysis. Preferably, P> 80%.

C can be determined using the "Y-Scale" option of the EVA software, by matching the peak intensities of the phase to be measured of the standard sample with those of the sample to be analyzed.

The ratio C is substantially the same whatever the peak considered, provided that this peak only concerns one of the metastrengite and strengite phases.

The rate of the phase considered in the sample to be analyzed is then classically determined by linear regression.

testing

The following examples are provided for illustrative purposes and do not limit the invention.

The raw materials used are as follows: ^β powder of Fe ₂ O ₃ iron oxide particles, whose purity is greater than or equal to 95% by weight and whose median size is equal to 0.3 μm,

• powder of MnO ₂ manganese oxide particles, whose purity is greater than or equal to 95% by mass and whose median size is equal to 53 μιη,

• phosphoric acid H ₃ P0 ₄ with a mass concentration equal to 85%,

Fe ₃ O ₄ iron oxide powder, "97% metal base -325 Mesh" marketed by Alfa Aesar,

• NH ₄ H ₂ P0 ₄ powder, whose purity is greater than or equal to 97% by weight.

The samples of Examples 1 to 7 are manufactured according to a process according to the invention:

Starting charges in step a) are provided by the following Table 1:

Starting load for producing the product according to the example:

Table 1

For each example, the iron oxide particle powder and / or the manganese oxide particle powder is disposed in the vessel of a VMI mixer R601 equipped with a sheet-shaped blade. The mixer is then started and the phosphoric acid is gradually added so as to obtain a homogeneous mixture.

The mixtures 1 to 7 thus obtained (for the manufacture of Examples 1 to 7, respectively) are transferred into silicone molds having a diameter equal to 24 cm and a height equal to 6 cm.

In step b), said molds are placed in a MEM ERT 749L 250 ° C UFP800 oven at 110 ° C for 12 hours. Once out of the oven, the blocks obtained are demolded and do not flow under their own weight after cooling.

The mixture 2 thus obtained is then transferred to a steel tank so that it can withstand a drying temperature of 400 ° C., said tank then being placed in a Nabertherm N500 / 65A oven at 400 ° C. for 2 hours. In step c), the blocks are crushed in a RETSCH BB200 crusher.

Comparative Example 8 is manufactured according to a process equivalent to the process for manufacturing the first compound ("first compound") described in Example 13 of EP 2 546 194: 4.64 grams of an iron oxide powder Fe ₃ 0 ₄ and 6.90 grams of a NH ₄ H ₂ PO ₄ ammonium phosphate powder are dry blended in a tungsten carbide mill. The ground mixture obtained is poured into a platinum boat. The nacelle is then placed in a tubular electric furnace and heated at a temperature of 1300 ° C for 30 minutes under a nitrogen atmosphere to melt the ground mixture. The molten mixture is then cooled by pouring into liquid nitrogen. The product obtained is amorphous and no crystalline phase could be demonstrated.

Comparative Example 9 is a metastrengite powder FePO ₄ .2H ₂ O sold by the company Budenheim.

The following Table 2 summarizes the properties of the products of Examples 1 to 7 obtained at the end of step c), as well as those of the products of Comparative Examples 8 and 9.

"Paf" refers to the loss on ignition, measured after heat treatment at 1000 ° C for 2 hours.

Table 2

The products of Examples 1 to 7, according to the invention, present:

a strengtte phase rate equal to 0, and

a metastrengite phase rate equal to 0.

The following table 3 summarizes the heterogeneity measurements obtained according to the method described above:

Table 3

The method described above makes it possible to demonstrate that the products according to Examples 1 to 7 have, after grinding, heterogeneous particles (but also homogeneous particles):

All the analyzed particles of the product according to Example 1 comprise first and second regions having first and second contents, T ₁ and T ₂ respectively, in element Fe and element P whose ratio T- | / T ₂ is greater than 1, 7, said particles all having first and second regions having first and second contents, Τ _Ί and T ₂ respectively, in element P whose ratio T ₁ / T2 is greater than or equal to 58.7.

All the analyzed particles of the product according to Example 2 comprise first and second regions having first and second contents, T, and T ₂ respectively, in element Fe and element P whose ratio Tj / T ₂ is greater than 1, 4, said particles all having first and second regions having first and second contents, ΤΊ and Τ ₂ respectively, in element P whose ratio Ti / T ₂ is greater than or equal to 24.3-

40% in number of the analyzed particles of the product according to Example 3 comprise first and second regions having first and second contents, T- and T _2, respectively, in Fe element and in element P whose ratio Ti / T ₂ is greater than 2.1, the said particles all having first and second regions having first and second contents, Ti and T ₂ respectively, P element whose ratio Ί ί ₂ is greater than or equal to 22.3.

All the analyzed particles of the product according to Example 4 comprise first and second regions having first and second contents, T and T _2, respectively, in element Fe and in element P whose ratio Ti / T ₂ is greater than 1, 4 said particles all having first and second regions having first and second contents, T ₁ and T _2, respectively, in Fe element whose ratio T 1 T ₂ is greater than or equal to 1.5.

All the analyzed particles of the product according to Example 5 comprise first and second regions having first and second contents, T- and T _2, respectively, in element Mn and element P whose Ti / T ratio ₂ is greater than 1 , 6, said particles all having first and second regions having first and second contents, T. and T ₂ respectively, in element P whose ratio T / T ₂ is greater than or equal to 12.2.

All the analyzed particles of the product according to Example 6 comprise first and second regions having first and second contents, T _f and T ₂ respectively, in element Mn, element Fe and element P whose ratio Τι Γ ₂ is greater than at 2.1, said particles all having first and second regions having first and second contents, Tt and T ₂ respectively, in Fe element whose ratio T ₁ / T ₂ is greater than or equal to 33.2.

All the analyzed particles of the product according to Example 7 comprise first and second regions having first and second contents, Ti and T ₂ respectively, in element Mn, element Fe and element P whose ratio Ti / T ₂ is greater at 6.5, said particles all having first and second regions having first and second contents, T, and T ₂ respectively, in Mn element whose ratio T, / T ₂ is greater than or equal to 27.5.

All analyzed particles of the product according to Comparative Example 8 and the product according to Comparative Example 9 are homogeneous and have first and second regions having first and second contents, T and T ₂ respectively, in Fe element and in element P whose ratio ΤΊ / Τ ₂ is equal to 1.

The following Tables 4 and 5 summarize the presence and amount of inciusions in the particles analyzed:

Tabieau 4

Table 5

The products of the examples according to the invention comprise at least 40% of particles comprising at least one inclusion. The products of Comparative Examples 8 and 9 do not include inclusion. The following starting raw materials were then intimately mixed in a mixer, from a stage A):

lithium carbonate powder Li ₂ CO ₃ , the purity of which is greater than 99% by weight and whose median size is less than 420 μm: 16.5% by weight,

product according to example 1 or 2: 83.5% by weight.

The initial charge, weighing 4 kg, was poured into a Herault-type arc melting furnace. During a step B), it was then melted following a melting with a voltage of 120 volts, an instantaneous power of 48 kW, and an applied energy substantially equal to 1200 kWh / T, in order to melt the entire starting load in a complete and homogeneous way. The fusion took place under air.

In step C), the liquid mass was then cast to form a net.

A compressed dry air blow, at room temperature and at an overpressure of 1 bar, broke the net and dispersed the molten liquid in droplets.

The blowing cooled these droplets and froze them in the form of melted particles.

Depending on the blowing conditions, the melted particles may be spherical or not, hollow or solid. They had a size between 0.005 mm and 5 mm.

The characteristics of the balls obtained are shown in Table 3 below:

The low loss of fire of the products according to the invention advantageously allows a very good control of the process of manufacturing materials rich in LAGJXODE phase (s), thus conferring on it a good reliability. As it is now clear, the product seion the invention, easily manipulated and without risk, allows the manufacture by melting phase rich materials (s) LAGJXODE, can be manufactured in industrial quantities and at a reduced cost.

Of course, the present invention is not limited to the described embodiments provided by way of illustrative and non-limiting examples.

In particular, the products according to the invention are not limited to particular shapes or dimensions.

Claims

1. Product with a loss on ignition at 100 ° C below 25% and, after loss on ignition, a chemical analysis such that, in percentages by mass and for a total of 100%:

- 17.0% <P <27.0%,

Fe + n such that the molar ratio (Fe + Mn) / P is such that 0.4 <(Fe + Mn) / P <1, 4, other elements than P, Fe, Mn, H and O <5.0 %

H + O: 100% complement,

the product comprising a phase, called "PO", other than strengite or metastrengite, said phase comprising elements oxygen and phosphorus on the one hand and the element iron and / or the manganese element on the other hand, and a crystallized phase and chosen

in the group G constituted by the crystallized phases of iron phosphates, the crystallized phases of manganese phosphates, the crystallized phases of mixed iron and manganese phosphates, or

in the group G _H constituted by the crystallized phases of iron hydroxides and the crystalline phases of hydroxides of manganese,

the crystallized phase may be the PO phase or not,

said product being such that, after optional grinding in the form of particles, more than 30% in number of the particles which have a size of between 106 μm and 250 μm are heterogeneous particles, a heterogeneous particle being a particle comprising, in a section of the particle, the first and second regions having first and second contents in the same element, ΤΊ and T ₂ respectively, such that the ratio T ₁ / T ₂ is greater than 1, 3, the element being Fe or Mn or P, the first and second regions each having an area greater than 1 Mm ² .

2. Product according to claim 1 being in the form of an agglomerates powder.

3. Product according to any one of the preceding claims, wherein after optional milling, more than 40% by number of the particles which have a size. between 106 pm and 250 pm are heterogeneous particles which have a ratio ΤΊ / Τ ₂ greater than 1, 7.

4. A product according to any one of the preceding claims, wherein after optional grinding, more than 30% by number of particles having a size of between 106 μm and 250 μm have at least one inclusion as one of said regions, an inclusion being a a region having a surface area of between 5 and 150 pm 2 and constituted, for more than 50% by weight, of the same element chosen from Fe, Mn and P.

5. A product according to any one of the preceding claims, wherein the mass content of Fe element is greater than 3.7% and the crystallized phase is selected from the group G ₀ and / or the group G _H and / or in ie the group consisting of the crystallized phases of manganese phosphates and the crystallized phases of mixed phosphates of iron and manganese.

6. Product according to any one of claims 1 to 4, comprising a crystallized phase selected from Fe ₂ 0 ₃ and / or Fe ₃ 0 ₄ and / or MnO and / or Mn ₂ 0 ₃ and / or Mn0 ₂ and / or Mn _3. 0 ₄ and / or Fe (OH) ₂ and / or FeO (OH) and / or Fe (OH) ₃ and / or n (OH) ₂ and / or MnPO ₄ and / or MnPO ₄ .nH ₂ O, n Being an integer greater than 0 and / or FePG ₄ and / or Fe ₃ H ₉ (PO ₄ ) ₆ .6H ₂ O and / or FeH ₃ P ₂ O ₈ , H ₂ O and / or FesH 2 PsO ₃ H ₂ O .

7. Product according to any one of claims 1 to 6, comprising a combination of a phase selected from the group G ₀ or the group G-, or from the group consisting of the crystallized phases of manganese phosphates and the phases crystallized mixed phosphates of iron and manganese, on the one hand, and a phase selected from the group consisting of crystallized phases of iron phosphates on the other hand.

8. Product according to claim 7, comprising a combination chosen from combinations of a phase selected from Fe ₂ 0 ₃ and / or Fe ₃ O ₄ and / or MnO and / or Mn ₂ 0 ₃ and / or nO ₂ and / or or Mn ₃ 0 ₄ and / or Fe (OH) ₂ , FeO (OH), Fe (OH) ₃ , Mn (OH) ₂ and / or MnPO ₄ , and / or MnP0 .nH ₂ 0, where "n" is a integer greater than 0 on the one hand, and a phase selected from FePO ₄ , and / or Fe ₃ H ₉ (PO ₄ ) ₆ .6H ₂ O, and / or FeH ₃ P ₂ O ₈ , H ₂ O and / or Fe ₃ H ₁₅ PsO _3z , 4H ₂ O on the other hand.

9. A product according to any one of claims 1 to 8, wherein the molar ratio (Fe + Mn) / P is greater than 0.5 and less than 1, 2.

The product of claim 9, wherein the molar ratio (Fe + n) / P is greater than 0.9 and less than 1.1.

1. The product according to any one of claims 1 to 10, wherein the loss on ignition is less than 20% and greater than 1%.

The product according to any one of claims 1 to 11, wherein the sum of the strengite and metastrengite phase levels is less than 80%, the strengite and metastrengite phase levels being the mass percentages of the metastrengite and strengite phase, respectively. , on all the crystallized phases of the product.

13. The product of claim 12, wherein the sum of the strengite and metastrengite phase levels is less than 5%.

14. Product according to any one of claims 1 to 4, and 9 to 13, having, after loss on ignition at 1000 ° C, a chemical analysis such that, in percentages by weight and for a total of 100%:

- 17.0% <P <22.0%,

- Fe <2.0%

Mn such that the molar ratio {Fe + n) / P is such that 0.9 <(Fe + Mn) / P <1, 1,

- other elements than P, Fe, Mn, H and O <5.0%,

- H + O: 100% complement,

said product comprising a crystalline phase other than the phases and strengite métastrengite and selected from the group G ₀ Mn consisting of crystallized phases of manganese oxides, or I group selected from G - ^■> :, ,, · consisting of crystallized phases of manganese phosphates, or selected from the group G _HMn constituted by the crystalline phases of manganese hydroxides.

15. Product according to any one of claims 1 to 4, and 6 to 13, having, after loss on ignition at 1000 ° C, a chemical analysis such that, in percentages by weight and for a total of 00%:

- 17.0% <P <22.0%,

- Mn <2.0% Fe such that the molar ratio (Fe + n) / P is such that 0.9 <(Fe + n) / P <1, 1

- other elements than P, Fe, Mn, H and O <5.0%,

- H + O: 100% complement,

said product comprising a crystallized phase (which may be the PO phase or not), other than the strengite and metastrengite phases and selected from the group G ₀ F _s constituted by the crystallized phases of iron oxides, or chosen from the group GPF _s consisting of crystalline phases of iron phosphates, or selected from GHF _¾ ie group consisting of crystallized iron hydroxides phases.

16. A product according to any one of claims 1 to 13, having, after loss on ignition, a loss on ignition at 1000 ° C of less than 25%, and, after loss on ignition, a chemical analysis such that, in percentages by weight and for a total of 100%:

- 17.0% <P <22.0%,

- (Fe + Mn) such that the molar ratio (Fe + n) / P is such that 0.9 <(Fe + n) / P <1.1, with the molar ratio Mn / Fe such that 2.3 <Mn / Fe <9,

- other elements than P, Fe, Mn, H and O <5.0%,

- H + O: 100% complement,

said product comprising a crystallized phase, other than strengite and metastrengite phases and selected from the group G ₀ consisting of crystallized iron oxide phases, crystallized manganese oxide phases, crystallized mixed oxide phases of iron and manganese or in the group G _P constituted by the crystallized phases of iron phosphates, the crystallized phases of manganese phosphates, the crystallized phases of mixed phosphates of iron and manganese or in the group G _H constituted by the crystallized phases of iron hydroxides, crystallized phases of manganese hydroxides.

17. Product according to any one of claims 1 to 13, having, after loss on ignition, a loss on ignition at 1000 ° Ο less than 25%, and, after loss on ignition, a chemical analysis such that, in percentages by weight and for a total of 100%:

- 17.0% <P <22.0%,

- (Fe + Mn) such that the molar ratio (Fe + Mn) / P is such that 0.9 <(Fe + Mn) / P <1.1, with the molar ratio Mn / Fe such that 0.6 <Mn / Fe <1, 5,

- other elements than P, Fe, Mn, H and O <5.0%,

- H + O: 100% complement, said product comprising a crystallized phase, other than the strengite and metastrengite phases and selected from the group G ₀ consisting of the crystallized phases of iron oxides, the crystallized phases of manganese oxides, the crystallized phases of mixed iron oxides and manganese or in the group G _P consisting of the crystallized phases of iron phosphates, the crystallized phases of manganese phosphates, the crystallized phases of mixed phosphates of iron and manganese or in the group G _H constituted by the crystallized phases of iron hydroxides, the crystalline phases of manganese hydroxides.

18. A product according to any one of claims 1 to 17, which is in the form of an assembly of solid particles bound by means of an asbestos phase-corresponding to a setting ensured by the reaction of phosphoric acid with phosphoric acid. iron oxide and / or iron hydroxide and / or manganese oxide and / or manganese hydroxide.

19. The product according to any one of claims 1 to 17, wherein: said crystallized phase is chosen:

if the molar ratio (Fe + Mn) / P is greater than or equal to 0.8:

if the molar ratio (Fe + Mn) / P is such that 0.4 <(Fe + Mn) / P <0.8:

20. A method of manufacturing a product according to any one of the preceding claims, iedit method comprising the steps of:

a) Means of a starting load comprising:

particles in an oxide and / or an iron hydroxide and / or

particles in an oxide and / or manganese hydroxide, and

a solution of phosphoric acid H ₃ PO _{4 having a} mass concentration of H ₃ PO ₄ greater than 60%, in a quantity such that the molar ratio (Fe + Mn) / P is between 0.4 and 1, 4,

all of said particles having a median diameter D _{50 of} less than 100 μm,

b) shaping and drying so as to obtain a product in the form of particles or a block, preferably in the form of a block,

c) optionally crushing and / or grinding and / or grinding,

d) optionally granulometric selection,

the composition of the feedstock and the drying being determined so that the particles or the block obtained at the end of step b) is a product according to any one of the preceding claims.

21. A method of manufacturing a cathode for lithium-ion battery comprising the manufacture of a product according to any one of claims 1 to 19, the preparation of a starting charge comprising said product, and the melting of said charge. starting so as to obtain a melted product.

22. The method of claim 21, comprising the manufacture of a cathode, from the obtained molten material.

23. A method according to any one of claims 21 and 22, wherein the feedstock is determined to obtain a molten material having at least one crystalline phase of formula (. _Aa) _x + _(b Gi- J _b) y [ (XQ ₄ ) i-aO <i] ze, or "phase LAGJXODE", in which:

Li is the lithium element,

A is a lithium substituent selected from the elements Na, K, H and mixtures thereof, a being less than or equal to 0.2,

G is selected from Fe, Mn, Ni, Co, V and their mixtures, J is a substituent of G selected from Nb, Y, g, B, Ti, Cu, Cr and mixtures thereof, b being less than or equal to 0.5,

X0 ₄ is an oxoanion in which O is the oxygen element and X is selected from P, S, V, Si, Nb, Mo and mixtures thereof,

D is selected from F ^" , OH ^" , CI ^" anions and mixtures thereof, d being less than or equal to 0.35,

E being selected from the element F, the element Cl, the element O, the group OH, and their mixtures,

0 <e≤ 2,

-0.2 <x <2,

0.9 <y <2,

1 <z <3.