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    • 专利摘要:
    A compound of the formula Li7-xPS6-xXx-z (BH4) z wherein X is selected from the group consisting of Cl, Br, I, F and CN 0 inf x = 20 inf z = 0.50. This compound can be used as solid electrolyte of a lithium-ion electrochemical element.
    公开号:FR3071656A1
    申请号:FR1758782
    申请日:2017-09-22
    公开日:2019-03-29
    发明作者:Christian Jordy；Pedro Lopez-Aranguren；Ha Anh Dao；Michel Latroche；Junxian ZHANG；Fermin CUEVAS
    申请人:SAFT Societe des Accumulateurs Fixes et de Traction SA；Centre National de la Recherche Scientifique CNRS；
    IPC主号:
    专利说明:

    SOLID ELECTROLYTE FOR LITHIUM-ION ELECTROCHEMICAL ELEMENT TECHNICAL FIELD
    The technical field of the invention is that of inorganic solid electrolytes for lithium or lithium-ion electrochemical cells. The technical field is also that of the processes for preparing such inorganic solid electrolytes.
    STATE OF THE ART
    Lithium-ion rechargeable electrochemical cells are known from the state of the art. Due to their high mass and volume energy density, they are a promising source of electrical energy for portable electronic devices, electric and hybrid vehicles and stationary electricity storage systems. However, these elements frequently contain an organic liquid electrolyte which, in the event of thermal runaway of the element, reacts in an exothermic way with the active matters of the negative and positive electrodes and in certain cases, the elements can catch fire, which constitutes a risk to the safety of the user.
    Lithium-ion rechargeable electrochemical cells comprising a solid electrolyte offer a solution to this risk of thermal runaway. By using a solid electrolyte, the exothermic reaction between the active ingredients and the electrolyte is suppressed, which considerably improves safety for the user. The solid electrolyte can be an inorganic compound.
    One of the main advantages of inorganic solid electrolytes is that they generally conduct a single type of ion, here, the Li + cation which is therefore exchanged with the active materials to ensure the electrochemical reactions. Few organic polymers used as solid electrolyte behave in the same way and when this is the case, their resistivity is greatly increased. Only Li + ions are therefore mobile for inorganic electrolytes. The other ions, anions and cations, are immobile. The lithium transport number is 1 (or tends to 1); this characteristic makes it possible to suppress the phenomena of ionic diffusion of the electrolyte, which improves the performance at fast regimes. Furthermore, inorganic electrolytes make it impossible to migrate chemical species in the thickness of the separator, which considerably reduces the self-discharge phenomena. Solid electrolytes widen the choice of electrode materials and can extend the potential window. The electronic conductivity must still be less than 10 '12 S / cm to accommodate storage for several months.
    When choosing an inorganic solid electrolyte, the resistance of the solid electrolyte at the electrode interface should also be taken into account because this resistance at the interface is just as important and is often as great as the resistivity of the electrolyte. For this reason, it is also necessary to take into account the contact resistance of particles to particles of electrolyte if it is a pulverulent material and not only that of the heart. Generally the resistance associated with ion exchange through the passivation layer (SEI) formed on the surface of the negative electrode will be higher than that of a liquid electrolyte or a polymer liable to deform.
    Work on highly conductive amorphous solid (glass) electrolytes based on lithium sulfide L12S, S1S2, P2S5 and B2S3 was reported in the early 1980s.
    The document J. Amer. Ceram. Soc. 84 (2001) 477 describes the manufacture by planetary grinding followed by compression of a mixture comprising 75% by mole of L12S and 25% by mole of P2S5. This mixture has an ionic conductivity at 25 ° C of 200 pS / cm.
    It is also known to use as a solid electrolyte of a lithium-ion electrochemical element a LiôPSsX compound of the argyrodite type where X denotes a halogen atom. This type of compound is obtained by reacting L12S with P2S5 and with a lithium halide LiX.
    Document JP 2016-134316 describes a solid electrolyte which is a mixture of a first sulfur-based compound, for example LiOPSsX, and a second compound which is a solid solution of LiX-LiBEL where X is a halogen. In this document, it is described that the particles of solid solution of LiX-LiBEL fill the empty volumes existing between the particles of the sulfur-based compound. The process for manufacturing the solid electrolyte in document JP 2016-134316 is carried out in several stages:
    - a first step of grinding a mixture containing L12S, P2S5 and LiX to form a LiôPSsX compound of the argyrodite type;
    - a second step of forming a solid solution of LiX-LiBEL;
    - a third stage of mixing products from the first and second stages. It can be noted that this preparation process does not allow the incorporation of BHy ions into the structure of the LiôPSsX compound.
    Document EP-A-3,043,411 describes an electrochemical element comprising a solid electrolyte. The solid electrolyte can consist of the superposition of two layers of different compositions. The first layer may comprise a material based on LÎ2S-P 2 S 5 . The second layer comprises a material which is a solid solution of LiX-LiBEL. As in document JP 2016-134316, the BEU 'ions are not incorporated into the structure of the material based on L12S-P2S5.
    We are looking for new compounds that can be used as solid electrolyte of a lithium-ion electrochemical element.
    We are also looking for a solid electrolyte with improved ionic conductivity.
    SUMMARY OF THE INVENTION
    To this end, the invention provides a compound of formula LÎ7-xPS6-xXx-z (BH4) z in which:
    X is selected from the group consisting of Cl, Br, I, F and CN;
    0 <x <2;
    0 <z <0.50.
    This compound is characterized by a partial substitution of the halide X ion by the borohydride ion BEU ’. It has a higher ionic conductivity than that of the compound LÎ7-xPS6-xXx in which the halide X is not substituted. The ionic conductivity can be multiplied by a factor of up to 7 when X is I and when the substitution rate is around 17%. The use of the compound according to the invention as solid electrolyte of a lithium-ion electrochemical cell makes it possible to reduce the internal resistance of the cell and allows the cell to supply a higher discharge voltage for a given discharge rate .
    According to one embodiment, x = l.
    According to one embodiment, X is I or Cl.
    According to one embodiment, 0.1 l <z <0.35.
    According to one embodiment, 0.1 l <z <0.20.
    According to one embodiment, 0.15 <z <0.20.
    According to one embodiment, the compound is in amorphous form.
    The subject of the invention is also a process for preparing the compound, said process comprising the steps of:
    a) provision of a mixture comprising L12S, P2S5, L1BH4 and LiX where X is chosen from the group consisting of Cl, Br, I, F and CN;
    b) grinding the mixture for a sufficient time to allow the incorporation of LiBEL into the compound LÎ7-xPS6-xXx-z (BH4) z.
    According to one embodiment, step b) of grinding is carried out for a duration of at least 15 hours, preferably at least 20 hours.
    The subject of the invention is also an electrochemical element comprising a solid electrolyte comprising the compound as described above.
    According to one embodiment, the solid electrolyte does not contain LiBEL.
    According to one embodiment, the electrochemical element further comprises:
    - at least one negative electrode comprising an active material chosen from the group consisting of carbon, tin, silicon, lithium and indium;
    at least one positive electrode comprising an active material chosen from the group consisting of lithiated oxides of transition metals and sulfur-containing compounds.
    According to one embodiment, the active material of the negative electrode is chosen from the group consisting of lithium and indium and the active material of the positive electrode is chosen from the group consisting of S, T1S2, T1S3, T1S4 , NiS, N1S2, CuS, FeS2, L12S, M0S3, polyacrylonitriles-sulfur, dithiooxamide and disulfide compounds.
    The subject of the invention is also a method of manufacturing an electrochemical element with a solid electrolyte, said method comprising the steps of:
    a) preparation of a mixture containing a positive electrochemically active material and optionally the compound as described above;
    b) deposition on the mixture obtained in step a) of a layer of the compound as described above to form a solid electrolyte;
    c) depositing at least one layer of a mixture containing a negative electrochemically active material and optionally the compound as described above on a free face of the layer of compound forming the solid electrolyte.
    Finally, the invention also relates to the use of an anion containing boron as a substituent of a halide ion in a compound of formula LÎ7- x PS6-xXx where X is chosen from the group consisting of Cl, Br, I , F and CN and 0 <x <2, to increase the ionic conductivity of this compound.
    DESCRIPTION OF THE FIGURES
    Figure 1 schematically shows the structure of a lithium-ion electrochemical cell as manufactured in the examples.
    "Li" and "In" respectively denote the lithium layer and the indium layer.
    "SE" refers to the solid electrolyte layer.
    "Positive" means the layer containing the positive active material.
    FIG. 2 represents the ionic conductivity of compounds of formula LÎ7-xPS6-xIx-z (BH4) z for different values of the rate of substitution of the halide ion L by the borohydride ion: 0%, 10%, 17%, 33% and 50%.
    FIG. 3 represents two X-ray diffraction spectra. The top spectrum is obtained with the compound of example 2. The bottom spectrum is obtained with the compound of reference example 1.
    FIG. 4 represents the X-ray diffraction spectra of samples A, B and C described in the experimental part. The bottom spectrum is obtained on sample A. The middle spectrum is obtained on sample B. The top spectrum is obtained on sample C.
    FIG. 5 represents the discharge curve at room temperature at the C / 20 regime of a lithium-ion electrochemical cell comprising a solid electrolyte of formula L16PS5C1o, 83 (B H4) o, 17.
    EXPLANATION OF EMBODIMENTS
    The compound according to the invention has the formula Li7- x PS6-xXx-z (BH4) z in which:
    X is selected from the group consisting of Cl, Br, I, F and CN
    0 <x <2
    0 <z <0.50.
    Preferably, the element X is I or Cl.
    This compound is characterized by a substitution of part of the halide ion X by the borohydride ion BEU '. This substitution has the effect of increasing the ionic conductivity compared to that of the compound Li7- x PS6-xXx not substituted.
    In one embodiment, x is greater than or equal to 0.1.
    In one embodiment, z is greater than or equal to 0.05.
    In one embodiment, z is less than or equal to 0.35.
    The Applicant has surprisingly observed that the increase in ionic conductivity was maximum when the substitution rate is in the range from 10 to 20% (0.1 l <z <0.20), preferably in the range ranging from 15 to 20% (0.15 <z <0.20). The ionic conductivity can be multiplied by seven thanks to this substitution.
    It was also observed that the increase in ionic conductivity was more marked when the compound was in an amorphous state. The advantages of an amorphous structure are isotropic conductivity, the ease of fabrication in dense thin layers. The compound can be subjected to a grinding step in order to increase its amorphous nature.
    It is preferable not to subject the compound to a heat treatment, such as an annealing, since this promotes the appearance of a crystalline structure. The examples in the experimental part illustrate the effect of the degree of crystallinity of the compound on its ionic conductivity.
    The compound according to the invention results from a chemical reaction between LiBEL and L12S, P2S5 and LiX. The process for preparing the compound according to the invention comprises the steps of:
    a) provision of a mixture comprising L12S, P2S5, L1BH4 and LiX where X is chosen from the group consisting of Cl, Br, I, F and CN;
    b) grinding the mixture for a sufficient time to allow the incorporation of LiBEL into the compound LÎ7-xPS6-xXx-z (BH4) z.
    It should be noted that according to the invention, the BEL borohydride ions are integrated into the structure Li7- x PS6-xXx during grinding. The grinding step is therefore carried out as long as lithium borohydride L1BH4 remains in the mixture, that is to say not yet incorporated in L17-xPS6-xXx. The duration of the grinding depends on the conditions under which the grinding is carried out (number of balls, internal volume of the jar, speed of rotation of the grinder, quantity of the starting mixture, etc.). A person skilled in the art will nevertheless easily be able to determine by routine tests whether lithium borohydride remains in the mixture. The X-ray diffraction technique can be used for this purpose to detect the presence of residual lithium borohydride.
    Preferably, the grinding is carried out for a period of at least 10 hours, preferably at least 15 hours, more preferably at least 20 hours.
    The grinding step is generally carried out under an inert atmosphere, for example under argon, and under a dry atmosphere.
    Preferably, the grinding step is carried out at room temperature.
    According to the invention, the grinding is carried out at one time on a mixture containing all the reagents L12S, P2S5, L1BH4 and LiX, in contrast to the process for manufacturing the solid electrolyte of document JP 2016-134316 in which one manufactures in a first the compound LiôPSsX; then in a second step the solid solution of LiX-LiBEL; and finally the mixture of LiôPSsX with LiX-LiBELi.
    The compound according to the invention can be used as a solid electrolyte. The thickness of the solid electrolyte layer can vary between 10 µm and 1 mm.
    The compound according to the invention can also be used in mixture with a negative active material of the electrochemical element and / or in mixture with a positive active material of the electrochemical element. Preferably, the compound according to the invention used in admixture with the negative active material or with the positive active material is identical to the compound used as a solid electrolyte.
    The positive active ingredient can be chosen from the group consisting of:
    a compound i) sulfur chosen for example from S, T1S2, T1S3, T1S4, M0S2, M0S3, FeS, FeS 2 , CuS, NiS, N1S2, N13S2, Li 2 S;
    a compound ii) of formula Li x Mni- y - z M ' y M z P04 (LMP), where M'and M are different from each other and are chosen from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Mn, Zn, Y, Zr, Nb and Mo, with 0.8 <x <1.2; 0 <y <0.6; 0 <z <0.2;
    - compound iii) of formula Li x M2-x- y -z-wM ' y MzM' w O2 (LM02), where Μ, Μ ', M and M' are chosen from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo, provided that M or M 'or M or M' is chosen from Mn, Co, Ni, or Fe;
    Μ, Μ ', M and M' being different from each other; with 0.8 <x <1.4; 0 <y <0.5; 0 <z <0.5; 0 <w <0.2 and x + y + z + w <2;
    - compound iv) of formula Li x Mn2- y - z M ' y M z O4 (LMO), where M' and M are chosen from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr , Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo; M 'and M being different from each other, and 1 <x <1.4; 0 <y <0.6; 0 <z <0.2;
    - compound v) of formula Li x Fei- y M y PO4, where M is chosen from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo; and 0.8 <x <1.2; 0 <y <0.6;
    - Compound vi) of formula xLÎ2MnO3; (l-x) LiM02 where M is chosen from Ni, Co and Mn etx <l;
    and a mixture of these compounds.
    The negative active ingredient can be chosen from the group consisting of:
    i) a carbon-based compound, such as graphite;
    ii) a lithiated titanium oxide, such as LÎ4TÎ5O12;
    iii) a metal chosen from lithium, indium, aluminum, silicon, tin and alloys containing these metals, preferably an alloy of lithium and indium.
    One or more binders can be added to the mixture containing the positive active material and the compound according to the invention. This binder can be chosen from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), an ethylene-propylene-diene rubber (EPDM), a styrene-butadiene rubber (SBR), polyvinyl alcohol, carboxymethylcellulose (CMC). Likewise, one or more binders can be added to the mixture containing the negative active material and the compound according to the invention. These binders can be the same as those chosen for the positive active material.
    A compound which is a good electronic conductor, such as carbon, can also be added to the mixture containing the positive active material and the compound according to the invention or can be added to the mixture containing the negative active material and the compound according to the invention.
    The mixture containing the positive active material and optionally one or more binders as well as the electronic conductive compound can be deposited on a current collector to thereby form a positive electrode. Likewise, the mixture containing the negative active material and optionally one or more binders as well as the electronic conductive compound can be deposited on a current collector to form a negative electrode.
    An “all solid” electrochemical element is obtained by superimposing at least one positive electrode, the solid electrolyte comprising the compound according to the invention and at least one negative electrode. The assembly can be obtained by compression.
    EXAMPLES
    Different argyrodite-type compounds have been synthesized. Their composition is shown in Table 1 below.
    Example Composition X z X Footnote 1 Li 6 PS 5 I 1.00 0.00 I Ex.l Li 6 PS 5 Io, 9o (BH 4 ) o, io 1.00 0.10 I Ex.2 L16PS5lo, 83 (BH4) o, 17 1.00 0.17 I Ex.3 L16PS5lo, 67 (BH4) o 33 1.00 0.33 I Ex.4 Li 6 PS 5 Io, 5o (BH 4 ) o, 5o 1.00 0.50 I Footnote 2 LiePSsCl 1.00 0.00 Cl Ex. 5 L16PS5C1o, 83 (BH4) o, 17 1.00 0.20 Cl
    Table 1: Compositions tested
    As a counterexample, a mixture comprising 83 mol% of Li LiPSsI and 17 mol% of L1BH4 was prepared.
    For the examples, the compounds are prepared by mechanosynthesis, that is to say a high energy mechanical-chemical grinding. The powders of the initial reagents L12S (Sigma Aldrich, 99.98%), P2S5 (Sigma Aldrich, 98%), L1BH4 (Rockwood Lithium, 97.8%), LiCl and Lil (Sigma Aldrich 99.99%) are mixed in stoichiometric quantities. For each synthesis, 1 g of mixture is placed in a 45 cm 3 stainless steel jar. 25 balls of 7 mm in diameter are also placed in the jar. It is sealed in argon in a glove box. The equipment used for grinding is a planetary mill of the Fritsch ™ brand, of the Pulverisette 7 type. The grinding time of the compounds according to the invention is 20 hours at a rotation speed of 600 rpm. These grinding conditions make it possible to carry out the chemical reaction between the various constituents.
    For the counterexample, the LiôPSsI compound is prepared as described above, then it is mixed in stoichiometric proportions with L1BH4 for 10 min at a speed of 300 rpm. These grinding conditions do not allow the substitution of part of T by BH4 ·.
    When the samples undergo a heat treatment, this consists of heating at 550 ° C for 5 hours in a sealed autoclave. This heat treatment causes recrystallization of the compound.
    X-ray diffraction analyzes are carried out on a Bruker ™ D8 Advanced type diffractometer using the Ka line of copper or molybdenum. A waterproof protection allows the analysis to be carried out under an argon atmosphere.
    The ionic conductivity measurements are carried out on pellets made from solid electrolyte powder. The preparation of the pellets consists of compressing solid electrolyte powder in a tableting mold under a pressure of 2 tonnes. The diameter of the tablet is 7 mm. The electrolyte tablet thus prepared is then inserted between two metallic lithium disks and the whole is placed in an electrochemical cell of Swagelok (TM) type . Conductivity measurements are made using a potentiostat type
    Autolab (TM) PGSTAT30 using a sinusoidal voltage of variable frequency between 1Hz and 1MHz and an amplitude of 10mV.
    Installation of electrochemical cells:
    The "all solid" electrochemical element is obtained by pressing three layers:
    - the first consists of a mixture containing the positive active material and the solid electrolyte,
    - the second consists of solid electrolyte only (this layer acts as a separator) and
    - the third consists of a negative electrode based on lithium and indium.
    - Preparation of the mixture containing the positive active material:
    The positive active ingredient used is titanium sulfide, T1S2. Its theoretical capacity is 239 mAh / g. This is mixed manually with solid electrolyte powder in an agate mortar in a glove box. The T1S2 compound being electronic conductor, the addition of conductive carbon is not necessary. The percentage of solid electrolyte in the mixture is 60%.
    - Preparation of the negative Li-In electrode:
    This consists of a 200 µm lithium metal layer on which a 100 µm indium layer is deposited.
    - Assembly step:
    A thin layer of mixture containing the positive active material is placed in a 9 mm diameter mold. A solid electrolyte layer is then deposited. A pressure of 2 tonnes is exerted using a press. We then obtain a tablet. On the electrolyte layer, the indium sheet is then deposited, then that of lithium. The assembly is tested in a Swagelok (TM) type electrochemical cell. The structure of the electrochemical element obtained is shown diagrammatically in FIG. 1.
    Results:
    Table 2 below collates the results of the ionic conductivity measurements. The results obtained for the compounds containing iodide (Reference examples 1 and examples 1 to 4) are represented graphically in FIG. 2. These results show that for a substitution rate of 10, 17, 33 and 50%, the conductivity ionic content of the compound is increased.
    Example Compound Ionic conductivity at room temperature (S / cm) % increase in conductivity compared to unsubstituted compound Footnote 1 LiePSsI Ι, ΟχΙΟ ' 4 0 Ex.l Li 6 PS 5 Io, 9o (BH 4 ) o, io 2, lxl0 ' 4 110 Ex.2 L16PS5lo, 83 (BH4) o, 17 7.5xl0 ' 4 650 Ex. 3 L16PS5lo, 67 (BH4) o 33 l, 3xl0 ' 4 30 Ex.4 Li 6 PS 5 Io, 5o (BH 4 ) o, 5o Ι, ΙχΙΟ ' 4 10 Footnote 2 LiePSsCl 1.5χ10 ' 5 0 Ex. 5 L16PS5C1o, 83 (BH4) o, 17 6.5xl0 ' 5 333 Counter-example 83% of LiePSsI + 17% of LiBH 4 8xl0 ' 5 -20
    Table 2: Result of ionic conductivity measurements (S / cm)
    It can be seen for the LiôPSsIi-zCBHQz family of compounds that the ionic conductivity exhibits a maximum as a function of the substitution rate of the Γ ion by the BELf ion. The optimal value of the substitution rate is between 10% and 33%, and close to 17%.
    The increase in ionic conductivity is also observed when element X is chlorine. Indeed, the compound of Example 5 has an ionic conductivity of 6.5 * 10 ' 5 S / cm while the compound of Reference Example 2 has an ionic conductivity of only 1.5 * 10' 5 S / cm. The substitution of 17% of Cl 'ions by BEL ions has made it possible to triple the ionic conductivity.
    These results were compared with that obtained for the counterexample which was prepared by simple mixing of the two LiOPSsI and LiBEL compounds. In this case, the conductivity of the mixture is lower than that of the LiôPSsI compound alone.
    In order to demonstrate that the BEL ′ ion is incorporated into the structure of the LiôPSsI compound, an X-ray diffraction spectrum was produced on the compound of Example 2 and on the compound of Reference Example 1. These two compounds have been subjected to a heat treatment so as to increase their crystallinity. FIG. 3 makes it possible to compare the spectrum of the compound of example 2 in which 17% of iodide has been replaced by the BEL ion with that of the compound of reference example 1.
    The spectrum of the compound of reference example 1 (bottom spectrum) has peaks attributable to the presence of the argyrodite phase with a cubic structure.
    The spectrum of the compound of example 2 (top spectrum) differs from that of reference example 1 mainly in that it shows spikes of low intensity attributable to a small amount of L12S used as reactant in the mixture. and who did not react. The peaks attributable to L12S are marked with asterisks (*). This spectrum also highlights the absence of LiBEL phase, which proves that the borohydride ion is integrated into the crystallographic structure of the compound LI6PS5lo, 83 (BH4) o, i7 during mechanosynthesis.
    Study of the influence of the degree of crystallinity of the compound on the ionic conductivity of the compound LÎ6PS5lo.83 (BH4) o.i7 (example 2) :
    A sample A has been prepared. It comes from the grinding of the mixture of reagents L12S, P2S5, Lil and L1BH4 for a period of 20 hours at a rotation speed of 600 rpm in the Fritsch planetary mill of the Pulverisette 7 type, under the conditions as described above. The grinding led to the formation of the compound of example 2. An X-ray diffraction spectrum was produced on this sample A. This spectrum is represented in FIG. 4 (bottom spectrum).
    Sample A was then heat treated at 550 ° C for 5 hours in a sealed autoclave to cause it to crystallize. A sample B is thus obtained. An X-ray diffraction spectrum was produced on this sample B. This spectrum is represented in FIG. 4 (spectrum of the medium).
    Sample B was then subjected to grinding to reduce its crystalline character. A sample C was thus obtained. An X-ray diffraction spectrum was produced on this sample C. This spectrum is represented in FIG. 4 (top spectrum).
    The spectrum of sample A shows only low intensity peaks corresponding to the presence of the L12S phase.
    The spectrum of sample B shows the low intensity peaks attributable to the presence of the L12S phase as well as the well defined high intensity peaks attributable to crystalline Li6PS5lo, 83 (BH4) o, i7.
    The spectrum of sample C shows that the L12S phase has almost disappeared. The peaks attributable to LI6PS5lo, 83 (BH4) o, i7 have decreased significantly in intensity, which indicates that the grinding stage has made a large amount of LI6PS5lo, 83 (BH4) o, i7 amorphous.
    The ionic conductivity of samples A, B and C was measured. The ionic conductivity values are given in table 4:
    Sample Summary conditions Crystalline state Width at mid-height of the peak located at an angle of 20 ° (*) Conductivity at room temperature (S / cm) AT crushed amorphous - 7.5xl0 ' 4 B ground and then heat treated fine lines cubic structure 0.2 ° 8xl0 ' 6 VS ground then heat treated and then ground cubic structure wide lines 0.8 ° 9xl0 ' 5
    * the angle is measured using the wavelength of molybdenum
    Table 4: Effect of crystallinity on the conductivity of the compound L6PS5lo, s3 (BH4) o, i7
    The measurements show that the highest ionic conductivity is obtained for the amorphous sample A. On the contrary, the lowest ionic conductivity is obtained for sample B in which LÎ6PS5lo, 83 (BH4) o, i7 is well crystallized. An intermediate conductivity value is observed for sample C which has a degree of intermediate crystallinity between the amorphous state and the crystalline state.
    The use of the compound according to the invention as a solid electrolyte makes it possible to reduce the voltage drop induced by the resistance of the separator. The following calculation demonstrates this advantage. In a lithium-ion electrochemical cell whose surface capacity of the electrodes would be 4 mAh / cm 2 and in which a separator layer 25 μm thick would consist of the compound of reference example 1 (LiôPSsI), the drop of voltage induced by the separator during a discharge at the speed of 10C is approximately 1 V according to the equations R = l / o. I / O with
    R: resistance of the separator (Ohm), σ: conductivity of the electrolyte (S / m), e: thickness of the separator (m), S: surface of the separator (m 2 ) and the voltage drop across the separator is equal at AU = R χ I, I being the current passing through the separator. This voltage drop is very significant because it represents 27% of the open circuit voltage of a lithium-ion electrochemical element comprising a positive electrode, the active material of which would consist of a lithiated oxide of nickel, cobalt and aluminum. (NCA) and comprising a negative electrode whose active material would consist of graphite. Indeed, the open circuit voltage of such an element is of the order of 3.6V. This voltage drop decreases to 0.13 V when the separator consists of the compound of Example 2: LI6PS5lo, 83 (BH4) o, i7. This value of 0.13 V is entirely acceptable since it only represents 3.6% of the open circuit voltage. Reducing this voltage drop allows the lithium-ion electrochemical cell to provide a higher voltage for a given discharge rate.
    conductivity (S / cm) separator resistance (ohm. cm 2 ) voltage drop due to the separator (V) Reference example 1 LiePSsI Ι, ΟχΙΟ ' 4 25 1 Example 2L16PS5lo, 83 (BH4) o, 17 7.5xl0 ' 4 3.33 0.13
    Table 3: Comparison between the voltage drop induced by a separator comprising the reference compound 1 and the voltage drop induced by a separator comprising the compound LI6PS5lo, 83 (BH4) o, i7 of Example 2.
    FIG. 5 represents for information the discharge curve at the C / 20 regime at room temperature of an electrochemical cell comprising:
    - a positive active ingredient based on T1S2;
    - A solid electrolyte consisting of the compound Li6PS5Clo, 83 (BH4) o, i7;
    - a negative active material based on indium and lithium.
    The mass capacity value measured in discharge at C / 20 is 238 mAh / g. It is almost equal to the theoretical capacity of T1S2 (239 mAh / g), which shows that the electrolyte works very well at room temperature.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    1. Compound of formula LÎ7-xPS6-xX x -z (BH4) z in which:
    X is selected from the group consisting of CI, Br, I, F and CN
    0 <x <2
    0 <z <0.50.
    [2" id="c-fr-0002]
    2. A compound according to claim 1, in which x = l.
    [3" id="c-fr-0003]
    3. A compound according to claim 1 or 2, wherein X is I or Cl.
    [4" id="c-fr-0004]
    4. Compound according to one of claims 1 to 3, in which 0.1 l <z <0.35.
    [5" id="c-fr-0005]
    5. Compound according to one of claims 1 to 4, in which 0, l <z <0.20.
    [6" id="c-fr-0006]
    6. Compound according to one of claims 1 to 5, in which 0.15 <z <0.20.
    [7" id="c-fr-0007]
    7. Compound according to one of the preceding claims, in amorphous form.
    [8" id="c-fr-0008]
    8. Process for the preparation of a compound according to one of claims 1 to 7, comprising the steps of:
    a) provision of a mixture comprising L12S, P2S5, L1BH4 and LiX where X is chosen from the group consisting of Cl, Br, I, F and CN;
    b) grinding the mixture for a sufficient time to allow the incorporation of L1BH4 into the compound L7- x PS6-xXx-z (BH4) z.
    [9" id="c-fr-0009]
    9. The preparation method according to claim 8, in which step b) of grinding is carried out for a period of at least 15 hours, preferably at least 20 hours.
    [10" id="c-fr-0010]
    10. An electrochemical cell comprising a solid electrolyte comprising the compound according to one of claims 1 to 7.
    [11" id="c-fr-0011]
    11. An electrochemical cell according to claim 10, in which the solid electrolyte does not contain LiBFU.
    [12" id="c-fr-0012]
    12. An electrochemical cell according to claim 10 or 11, further comprising:
    - at least one negative electrode comprising an active material chosen from the group consisting of carbon, tin, silicon, lithium and indium;
    at least one positive electrode comprising an active material chosen from the group consisting of lithiated oxides of transition metals and sulfur-containing compounds.
    [13" id="c-fr-0013]
    13. An electrochemical cell according to claim 12, in which:
    - the active material of the negative electrode is chosen from the group consisting of lithium and indium;
    - the active material of the positive electrode is chosen from the group consisting of S, T1S2, T1S3, T1S4, NiS, N1S2, CuS, FeS2, L12S, M0S3, polyacrylonitriles-sulfur, dithiooxamide and disulfide compounds.
    [14" id="c-fr-0014]
    14. Method for manufacturing an electrochemical element with a solid electrolyte, said method comprising the steps of:
    a) preparation of a mixture containing a positive electrochemically active material and optionally the compound according to one of claims 1 to 7;
    b) deposition on the mixture obtained in step a) of a layer of the compound according to one of claims 1 to 7 to form a solid electrolyte;
    c) depositing at least one layer of a mixture containing a negative electrochemically active material and optionally the compound according to one of claims 1 to 7 on a free face of the layer of compound forming the solid electrolyte.
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    同族专利:
    公开号 | 公开日
    JP2020534245A|2020-11-26|
    WO2019057840A1|2019-03-28|
    CN111213274A|2020-05-29|
    US20200227776A1|2020-07-16|
    KR20200090739A|2020-07-29|
    FR3071656B1|2019-10-11|
    EP3685466A1|2020-07-29|
    EP3685466B1|2021-09-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20160156064A1|2013-07-25|2016-06-02|Mitsui Mining & Smelting Co., Ltd.|Sulfide-Based Solid Electrolyte for Lithium Ion Battery|
    KR102272556B1|2013-09-02|2021-07-02|미츠비시 가스 가가쿠 가부시키가이샤|Solid-state battery|
    JP2016134316A|2015-01-20|2016-07-25|出光興産株式会社|Solid electrolyte|CN110112457A|2019-05-23|2019-08-09|桑德新能源技术开发有限公司|A kind of all-solid-state battery and preparation method thereof|
    CN110120510B|2019-05-23|2021-07-13|桑德新能源技术开发有限公司|All-solid-state battery and preparation method thereof|
    WO2021085238A1|2019-10-29|2021-05-06|三井金属鉱業株式会社|Solid electrolyte, and electrode mixture, solid electrolyte layer and solid-state battery, each using same|
    WO2021085235A1|2019-10-29|2021-05-06|三井金属鉱業株式会社|Solid electrolyte, and electrode mixture, solid electrolyte layer and solid-state battery, each using same|
    WO2021085239A1|2019-10-29|2021-05-06|三井金属鉱業株式会社|Solid electrolyte, and electrode mixture, solid electrolyte layer and solid-state battery, each using same|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1758782A|FR3071656B1|2017-09-22|2017-09-22|SOLID ELECTROLYTE FOR LITHIUM-ION ELECTROCHEMICAL ELEMENT|
    FR1758782|2017-09-22|FR1758782A| FR3071656B1|2017-09-22|2017-09-22|SOLID ELECTROLYTE FOR LITHIUM-ION ELECTROCHEMICAL ELEMENT|
    US16/648,329| US20200227776A1|2017-09-22|2018-09-20|Solid electrolyte for a lithium-ion electrochemical cell|
    KR1020207008261A| KR20200090739A|2017-09-22|2018-09-20|Solid electrolyte for lithium ion electrochemical cells|
    EP18769383.3A| EP3685466B1|2017-09-22|2018-09-20|Solid electrolyte for a lithium-ion electrochemical element|
    JP2020537861A| JP2020534245A|2017-09-22|2018-09-20|Solid electrolyte for lithium ion electrochemical cell|
    PCT/EP2018/075516| WO2019057840A1|2017-09-22|2018-09-20|Solid electrolyte for a lithium-ion electrochemical element|
    CN201880061262.5A| CN111213274A|2017-09-22|2018-09-20|Solid electrolyte for lithium-ion electrochemical cells|
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