Patent Application
20190211422
The present invention relates to the field of energy storage and more particularly to that of composite intermetallic negative electrodes.
The new storage devices must contribute to the optimised management of energy enabling the integration of renewable energies into the energy mix. With regard to Li-ion accumulators, future systems must have much higher energy densities while also being safer with increasingly longer cycle and calendar lifetimes depending on applications (stationary, space, transport).
With regard to negative electrodes, intermetallic materials that are made from tin (Sn) or silicon (Si) are generally envisaged. They display high energy densities (600 to 4000 Ah/kg) but have significant aging related problems linked to several phenomena:
It is therefore essential both to control the volume expansion during the formation of LixSn or LixSi alloys and to absorb this expansion, as well as to protect the electrode from chemical etching.
In order to minimize the aforementioned degradation phenomena, several approaches have been developed (nanostructuring, dispersions, passivation layers).
The composite alloys of the Ni—Ti—Sn system have a broad cyclability range (in particular from 40 atomic % Sn) and good adhesion to the phosphate passivation layer generally applied in metallurgy. However their high atomic mass may be a handicap to achieving interesting mass capacities.
The composite alloys of the Ni—Ti—Si system are active only from 60 atomic % of Si. The existence of active and inactive Si-based particles is of interest for reducing the mechanical degradation and the low atomic mass largely compensates for the loss of active species. However, the material generally has poor adhesion to the passivation layer, and chemical degradation, although delayed, is inevitable after a certain number of cycles.
The solutions proposed still continue to not be fully satisfactory.
The inventors have thus identified that Ni—Ti—Si/Sn mixed composites having a high Si content thus make it possible to achieve greater capacity and good absorption of volume variations, and combined with more deformable Sn alloys, enable the adherence of the phosphate passivation layer. They therefore represent a solution to the problems encountered.
The present invention therefore provides novel electrode materials obtained by dispersing the active species (Sn, Si, Sn/Si) in a Ti—Ni—(Sn/Si) composite matrix, of multi-scale polycrystalline ceramic or glass-ceramic types, that present a large number of advantages (domains of distributed complex compositions with a medium-range order, possibility of combining different properties, ease of synthesis). In particular, these materials combine several properties: a high energy density with minimized volume expansion (Hume-Rothery intermetallics), an absorption of the residual volume expansion by dispersion of the active species in deformable inactive species systems, referred to as “shape memory”, as well as stable passivation thanks to Ni2SnP type flexible solders.
The composite materials according to the invention therefore make it possible to: 1) minimize the volume expansion by means of a predictive model; 2) absorb the remaining volume variations by dispersing the active species in multi-scale polycrystalline composite systems or glass-ceramics in which certain compounds have “shape memory” and 3) possibly fixing these domains and protecting them with protective layers bonded by flexible welds by means of a synthetic passivation layer subsequently formed by interaction between the composite and the passivating system.
As used herein, the term “composite” is understood within the meaning of the present invention to refer to an assembly of at least two compounds that are immiscible (but having a high penetration capacity) whose properties complement each other. The novel material thus constituted, is heterogeneous, having properties that the compounds alone do not possess. More particularly, the said material may be formed of at least two defined compounds or elements, of different nature and/or dimensions, which behave as a single compound by virtue of an assembly that imposes a medium-range order. This arrangement then makes it possible to add the properties of the compounds without modifying them. The composite may be multi-scale polycrystalline, or glass-ceramic, vitreous.
According to a first object, the present invention relates to a composite material enriched with electrochemically active Si, having the formula (I-M):
(1−z)M+zSi (I-M)
NixTiySn1−(x+y) (M1)
Nix′Tiy′Si1−(x′+y′) (M2)
M3=aM1+(1−a)M2
In the case where the dispersion composite matrix is the matrix M1, the enriched composite material according to the invention then corresponds to the formula (I-M1):
(1−z)M1+zSi (I-M1)
Nix(1−z)Tiy(1−z)Sn(1−z)(1−x−y)Siz (I-M1)
In the case where the dispersion composite matrix is the matrix M2, the enriched composite material according to the invention corresponds to the formula (I-M2):
(1−z′)M2+z′Si (I-M2)
Nix′(1−z′)Tiy′(1−z′)Si1−(x′+y′)(1−z′) (I-M2)
In the case where the dispersion composite matrix is the matrix M3, the composite material enriched according to the invention, corresponds to the formula (I-M3):
(1−z″)M3+z″Si (I-M3)
Ni[x′+a(x−x′)](1−z″)Ti[y′+a(y−y′)](1−z″)Sna(1−x−y)(1−z″)Si(1−a)(1−x′−y′)(1−z″)+z″ (I-M3)
In order to minimize volume expansion a prediction model has been established on the basis of the HUME-ROTHERY studies, showing that metal systems of equivalent electron concentrations [e] are able adopt several compositions without deformation of the network. For tin-based materials these electron concentrations [e], involving only localized valence electrons, are directly related to Mössbauer isomeric shifts.
This predictive experimental model makes it possible to minimize the volume expansion by synthesizing the alloys that are placed in the domain that present electron concentrations [e] corresponding to the alloys rich in lithium LixSn (x˜3 to 4.2).
In order to absorb the still existing volume variations, the electrochemically active alloys have been combined with “shape memory” alloys, having the overall formula NiTiMeu (Me=Si, Sn; u≤1). These alloys have an electron concentration that is sufficiently low (<1.5) so as not to be involved in the electrochemical process. These various active and inactive compounds are combined, the assembly thereof thus constituting the intermetallic composite material with specific properties (minimization and absorption of the volume expansion).
The composite material enriched according to the invention can be protected from chemical degradation in order to prevent the direct contact of the environment such as the electrolyte with the surface of the material.
Thus, the protection of the composite electrode vis-à-vis the electrolytic environment during the galvanostatic cycles of charging/discharging is ensured thanks to a coating of alkaline phosphates, the nickel reducing properties making it possible to ensure good adhesion between the protective layer and the composite while also ensuring a better contact with the current collector thanks to the formation of phosphides of Ni, Sn of type Ni2SnP/Ni10Sn5P3 used as flexible solder in semiconductors.
According to another object, the invention therefore also relates to the said passivated enriched composite material (I-M), comprising:
The term “surface passivation layer” is used to refer to a thin, stable, electronically insulating and ionically conductive layer that can be applied to a material in order to prevent direct contact of the said material with its environment. Typically, the said passivation layer can be likened to a layer referred to as sold/electrolyte interface layer (SEI).
The passivation layer may be selected from among the layers usually used to protect the intermetallics. The enriched composite material that is possibly passivated according to the invention, is particularly suitable as an electrode material.
According to another object, the present invention therefore also relates to an electrode comprising:
Original matrices M have been developed so as to prepare the composite materials of the invention.
NixTiySn1−(x+y) (M1)
According to one embodiment, the dispersion composite matrix having the formula (M1) here above advantageously comprises the elements Ti, Ni, Sn in the following proportions (in atomic percentages):
According to one embodiment, the dispersion composite matrix having the formula (M1) here above typically corresponds to the formula:
Ni(3+n)tTi6(1−t)Sn(5−t)
Where n is comprised between 0.3 and 0.7 and t is comprised between 0.50 and 0.75.
According to another object, the present invention also relates to the dispersion composite matrix having the formula (M3)
Nix′+a(x−x′)Tiy′+a(y−y′)Sna(1−x−y)Si(1−a)(1−x′−y′) (M3)
The present invention also relates to the preparation method for preparing the enriched composite material having the formula (I-M).
Typically, the synthesis method for synthesizing matrices is reactive grinding, carried out under conditions that are adjusted to the systems and to the composition domains. The grinding conditions generally depend on parameters such as rotational speed, ratio of powder mass/bead mass. Generally, these parameters are respectively 500 revolutions/minute for the speed of rotation, a ratio of about 1/28 for 15 mm diameter beads, it being understood that the grinding time comprised between 200 and 700 in particular, may be adapted according to the composition domain. Generally, the composites enriched with silicon may be synthesized by grinding in the liquidus domain. The term “reactive grinding” is understood herein to refer to the grinding of at least two compounds interacting with each other during the grinding, and resulting in a synthesized final composite material that is generally thermodynamically stable.
Two lanes may thus be used: i) by dispersion of the silicon in the preformed matrices M with compositions corresponding to the binary systems (1−z) M1−z Si and (1−z′) M2−z′ Si, (1−z″)M3−z″Si; or ii) by integration of the silicon from the compounds, binary for tin (Ni3+nSn4 where n is comprised between 0.3 and 0.7, Ti6Sn5, Si); and from the elements (Ni, Ti, Si) for silicon with the same compositions as those of the lane i.
The step of grinding may generally be carried out for any mechanical method usually used, by application of procedures generally known to the person skilled in the art.
Typically, according to a first embodiment, the said method comprises the step of grinding of Si with the said dispersion composite matrix M, by means of z part of Si and (1−z) part of the said dispersion composite matrix M, where z is as defined here above.
According to another embodiment, the said method comprises the grinding of Si with the other elements constituting the composite matrix or with the alloys containing the said elements.
According to one embodiment, when the said enriched composite material (I-M2) does not contain Sn, then the method comprises grinding the elements Si, Ti, Ni in stoichiometric proportions.
According to another embodiment, when the enriched composite material (I-M) contains Sn, the said method comprises the grinding of Si with the alloys Ni3+nSn4 and Ti6Sn5 where n is comprised between 0.3 and 0.7.
According to another object, the present invention relates to the preparation method for preparing the passivated enriched composite material (I-M) above. The said method generally comprises the placing in contact of the enriched composite material (I-M) with an aqueous solution of alkali metal phosphate, which may optionally be hydrated.
The placing in contact may be carried out by suspension or immersion of the material in the said aqueous solution or by application and/or spreading of the said solution over the said material.
Typically, the said mixture is produced in an acidic medium, at a temperature comprised between 20 and 80.
According to the invention, novel original methods have been developed for preparing the matrices M1, M2 and M3.
It involves the synthesizing of the stable composite intermetallic matrices M1, M2 and/or M3 thus enabling the dispersion of the active species Si.
The present invention therefore also relates to the preparation method for preparing the dispersion composite matrix having the formula (M1) comprising the grinding of the alloys Ni6+nSn4 and Ti6Sn5 where n is comprised between 0.3 and 0.7.
Generally, the said method comprises the step of grinding of the alloys Ni3+nSn4 and Ti6Sn5 in the molar ratio (Ni3+nSn4)/(Ti6Sn5)=t/(1−t) where n is comprised between 0.3 and 0.7 and t is comprised between 0.50 and 0.75.
According to another object, the present invention also relates to the preparation method for preparing the dispersion composite matrix (M2) comprising the grinding of the elements Ni, T and Si in stoichiometric proportions.
According to another object, the present invention also relates to the preparation method for preparing the dispersion composite matrix (M3) by grinding the alloys Ni3+nSn4 where n is comprised between 0.3 and 0.7 and Ti6Sn5, and the elements Ti, Ni and Si.
The present invention is illustrated here below by means of illustrative and non-limiting examples of embodiments.
a) Matrices M1
In order to avoid the premature melting of Sn (232° C.) during grinding, the tin-based matrices are synthesized from the pseudo-binary t Ni3+nSn4-(1−t) Ti6Sn5 having the overall formula Ni3.6tTi6(1−t)Sn5−t for different values of n comprised between 0.3 and 0.7, and t comprised between 0.50 and 0.75 (
These different matrices are synthesized by reactive grinding under the same conditions (nature of jars, rate of filling, number of beads) with three grinding times (1 hr, 3 hrs, 10 hrs) in order to follow the evolution of the reactions. It is found that the 1 hr grinding corresponds to a phase of redistribution of the starting materials with probably a creation of interfaces observable by the widening of some X-ray diffraction lines. The grinding times of 3 hrs and 10 hrs show little structural differences and constitute reactive phases leading to a composite distributed differently according to the composition.
The matrix M1 of the global composition Ni0.277Ti0.227Sn0.496 corresponding to n=0.60 t=0.67 obtained after 3 hours of effective grinding is the most interesting. The X-ray diffraction characteristic of a highly divided material makes it possible to identify an inactive compound TiNiSn and domains that are more amorphized, modified active compounds of types Ni3Sn4 and Ti6Sn5. Mössbauer spectrometry confirms the presence of 23% of electrochemically inactive TiNiSn and 77% of active compounds.
This matrix M1 was electrochemically tested as a button cell from electrodes developed in the form of an ink constituted of the active material (70%)+carbon Y50A (18%)+CMC (12%) coated on a copper collector [Cycling conditions: C/10; potential window 1.5 V-0.01 V, Electrolyte free of additive]. It is electrochemically active with a reversible capacity of 393 Ah/kg. This reversible capacity is in agreement with the presence in this composite of 23% of inactive species of the type TiNiSn.
b) Matrix M2
The melting point of silicon being high (1410° C.) the syntheses are carried out by grinding of the elements. The composition consisting of 26.7 at % of Ti, 26.7 at % of Ni, and 46.6 at % of Si having the overall formula Ni0.267Ti0.267Si0.466 (
The X ray diffraction diagram shows the presence of the phase Ti4Ni4Si7. The broadening of the diffraction lines reflects the small size of the particles.
This matrix is electrochemicaly inactive (
c) Matrix M3
The matrix M3=a M1+(1−a) M2 with a=0.25 having the overall formula Ni0.27Ti0.26Sn0.12Si0.35 was synthesized by 20 hrs of grinding of the mixture [0.25 M1+0.75 M2] M1 and M2 being obtained according to the methods described here above in 1a and 1b. The X-ray diffraction makes clearly evident the presence of crystallized β Sn and of the amorphized species of the ternary system Ti—Ni—Sn. Mössbauer spectrometry confirms the presence of β Sn, and shows the presence of a ternary compound that is electrochemically inactive and deformable and an active compound. In electrochemical analysis (
a) Composites I-M1 (M1 Enriched with Si) (Lane i)
The lane i consists in being placed on the binary system (1−z) M1−z Si. The composition N0.276Ti0.227Sn0.497, situated in the liquidus zone (
The synthesis was carried out by grinding the mixture of 0.87 M1+0.13 Si for a period of 3 hrs. The material obtained was characterized by X-ray diffraction, Mössbauer spectrometry and electrochemistry.
After grinding, the X-ray diffraction lines of the silicon are broadened and of low intensity.
The Mössbauer spectrum presents three sub-spectra, two major doublets corresponding to the active compounds (δ=2.09 mm/s, Δ=1.72 mm/s and δ=2.04 mm/s, Δ=0.76 mm/s) and one singlet (δ=1.52 mm/s) attributable to a stable ternary phase of type TiNiSn which is inactive in electrochemistry. The hyperfine parameters of the doublets substantially different from those observed for Ni0.276Ti0.227Sn0.497 would suggest that a part of the silicon has been integrated into the dispersion matrix M1.
The electrochemical tests show a reversible capacity ˜425 Ah/kg and a good cycle life performance over the 30 cycles performed. This reversible capacity that is lower than the theoretical capacity (670 Ah/kg) confirms that the silicon integrated into the matrix M1 is electrochemically inactive.
b) Composites I-M1 (M1 Enriched with Si) (Lane ii)
In order to verify the possibility of integration of the silicon into the matrix M1 the enriched composite I-M1 having the same overall formula as that described here above in 2a was synthesized from the binary phases of tin (Ni3.6Sn4 and Ti6Sn5) and from the silicon element according to lane ii. Thus the mixture 0.067 Ni3.6Sn4+0.033 Ti6Sn5+0.13 Si was ground for a period of 3 hrs.
In X-ray diffraction the diagram before grinding is characteristic of the three compounds (Ni3.6Sn4, Ti6Sn5, Si). After grinding, the amorphization of the material is quite significant, the lines of diffraction of the silicon have disappeared and the diffractogram is characteristic of a composite that is different from the one obtained by the lane i. Similarly, the Mössbauer spectrum is formed by a single doublet with hyperfine parameters (δ=2.04 mm/s and Δ=1.13 mms) that are different from those of the composite obtained by the lane i. These two techniques show that the silicon has been homogeneously integrated into the matrix.
In electrochemical analysis (
c) Composites I-M2 (M2 Enriched with Si) (Lane i)
The composites I-M2 enriched with silicon are obtained by being placed on the system (1-z′) M2+z′ Si. The composition of M2 selected for the enrichment, situated in the liquidus zone (
d) Composites I-M2 (M2 Enriched with Si) (Lane ii)
The same composition Ni0.12Ti0.12Si0.76 was synthesized by grinding the elements (lane ii) with an effective grinding time of 12 hrs.
The resulting composite obtained was characterized by X-ray diffraction and electrochemical analysis. In X-ray diffraction, the majority presence of silicon and compounds of type Ti5Si3 or NiTi4Si4 and Ni2Si2 was identified just as for the lane i. In electrochemical analysis (
e) Composite I-M3 (M3 Enriched with Si)
The composite I-M3 was synthesized by grinding for a period of 20 hours of the matrix M3 having the overall composition Ni0.27Ti0.26Sn0.12Si0.35 obtained by the method described in Example 1.c and the silicon element with the proportions 0.57 Ni0.27Ti0.26Sn0.12Si0.35+0.43 Si leading to the overall formula Ni0.15Ti0.15Sn0.07Si0.63.
For the Composite I-M3 enriched with silicon the X diffraction makes clearly evident the presence of β Sn, Si and of the amorphized species of the system Ti—Ni—Sn—Si. In Mössbauer spectrometry the presence of β Sn is confirmed, with the presence of an electrochemically active species. The enrichment with silicon significantly improves the reversible capacity (511 Ah/kg,
Protection of the composite electrode vis-à-vis the electrolytic environment during the galvanostatic charge/discharge cycles is ensured by applying a coating of alkaline phosphates, the nickel reducing properties making it possible to ensure good adhesion between the protective layer and the composite while also ensuring a better contact with the current collector thanks to the formation of ternary phosphides of type Ni2SnP used as flexible solder in semiconductors.
Ni2SnP known for its deformable properties is formed in situ by reaction between the phosphate passivation layer and the composite thanks to the catalytic properties of the nickel released during the grinding of Ni3+nSn4 with n comprised between 0.30 and 0, 70. The composites are passivated with a solution of acidified sodium phosphate at pH=2. This solution is prepared from sodium phosphate monohydrate (NaH2PO4, H2O) at a concentration of 90 g/L (between 40 and 140 g/l). After dissolution of the phosphate in water, the solution is then acidified with orthophosphoric acid (H3PO4) until obtaining a pH equal to 2 (between pH=1.5 and pH=2.5). In order to passivate the composites, the latter are mixed with the phosphate solution and placed in a bath thermostated at 40° C. (between 20 and 80° C.) for a period of 4 hours, with magnetic stirring or bubbling (flow of nitrogen through a sinter). After reaction, the passivated composite is recovered by filtration on Büchner devices, and then dried under vacuum at 80° C. for a period of 12 hours. The product thus obtained is then used as electrode material.
a) Protection of the Composite I-M1 (Lane ii)
The composite I-M1 (Lane ii) was prepared by grinding for a period of 3 hours of the mixture 0.067 Ni3.6Sn4+0.033 Ti6Sn5+0.13 Si corresponding to the overall formula Ni0.241T0.197Sn0.432Si0.13. The passivation thereof was carried out according to the method previously described above and one of the passivated samples was heat-treated at 250° C. under argon. These three materials were electrodeposited in the form of inks of active material composition (70%)+carbon Y50A (18%)+CMC (12%) coated on a copper collector and tested in electrochemical analysis [Cycling conditions: C/10; potential window 1.5 V-0.01 V, Electrolyte free of additive] (Table 1).
These results are illustrated in
Protecting the composite I-M1 does not modify the nature of the material. The surface layer results in a slight increase in loss in the 1st cycle and an increase in polarization. The decrease in cycling capacity results from the involvement of tin in the passivation layer, resulting in a slight improvement in coulombic efficiency. The effect of the heat treatment is manifested by a noticeable decrease in the polarization as a consequence of greater adhesion with preserved coulombic efficiency.
b) Protection of the Composite I-M2 (Lane ii)
Composite I-M2 (Lane ii) was prepared by grinding for a period of 12 hrs of the mixture of 12% Ti, 12% Ni and 76% Si corresponding to the overall formula Ni0.12T0.12Si0.76. The passivation thereof was carried out according to the method described here above. These two materials were electrodeposited in the form of inks of active material composition (70%)+carbon Y50A (18%)+CMC (12%) coated on a copper collector and tested in electrochemical analysis [Cycling conditions: C/10; potential window 1.5 V-0.01 V, Electrolyte free of additive] (Table 2).
These results are illustrated in
The enrichment with silicon of the matrix M2 (electrochemically inactive) leads to remarkable electrochemical performance measures (Table 2). Protecting the silicon enriched composite M2 does not improve these performance measures. These results show that silicon is not strongly involved in the protective layer which proves to be inoperative. By comparison with the results obtained for the composite M1, it is apparent that tin thus plays a role in the effectiveness of passivation.
c) Protection of the Composite I-M3 [0.25 M1 (Lane ii)+0.75 M2 (Lane ii) Enriched with Si]
The composite I-M3 was synthesized by grinding for a period of 20 hrs of the mixture 0.57 M 3+0.43 Si leading to the overall formula Ni0.153Ti0.146Sn0.071Si0.630.
These results are illustrated in
The passivation of the silicon-enriched composite M3a consumes a portion of the tin as is shown by the X-ray diffraction pattern. As a result, the cycling capacity decreases (Table 3). Tin is therefore indeed involved in the passivation layer and coulombic efficiency is significantly improved (99.7%).
In the composite M1 (NixTiySn1−(x+y) with 0.20≤x≤0.30 and 0.20≤y≤0.30) tin is active in cycling. The enrichment with silicon is possible but it is more or less integrated into the composition domain of the matrix M1 and becomes inactive. The tin contained in the matrix M1 remains active but is not sufficiently protected from the causes of aging. The enrichment with silicon improves the mechanical strength of the composite electrode due to the inactivity of the silicon-containing compound. The passivation consumes approximately 10% of the tin and thus the tin directly participates in the adhesion of the passivation layer of the composite. Whereas the reversible capacity is slightly decreased the coulombic efficiency is significantly improved. For this type of composite the capacity remains insufficient.
In the composite M2 (Nix′TiySi1−(x′+y′) with 0.20≤x′≤0.30 and 0.20≤y′≤0.30) the formation is observed of a defined nanostructured compound Ni4Ti4Si7 which is already identified in the literature. This composite is virtually inert electrochemically. The enrichment with Si corresponds to a global composition of 76 atomic % silicon substantially above the 60% defined as the limit of the inactive composite M2. The electrochemical performance measures are remarkable (870 Ah/kg cycling) with an interesting level of coulombic efficiency (99.7%). The passivation does not improve electrochemical performance. Tin therefore plays a role in the effectiveness of passivation.
In the mixed composite M3a (0.25 M1+0.75 M2) the capacity is relatively low due to the composition Sn+Si<60% with as a consequence the inactivity of silicon. However the polarization is very weak and the coulombic efficiency is high (99.7%). The enrichment with silicon corresponding to the compositions Sn+Si˜70% improves the cycling capacity. Passivation consumes a part of the tin which significantly improves coulombic efficiency.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1654484 | May 2016 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/062046 | 5/18/2017 | WO | 00 |
