EP4179590A1 - Membran aus einem polykristallinen llzo-produkt - Google Patents

Membran aus einem polykristallinen llzo-produkt

Info

Publication number
EP4179590A1
EP4179590A1 EP21739688.6A EP21739688A EP4179590A1 EP 4179590 A1 EP4179590 A1 EP 4179590A1 EP 21739688 A EP21739688 A EP 21739688A EP 4179590 A1 EP4179590 A1 EP 4179590A1
Authority
EP
European Patent Office
Prior art keywords
less
elements
membrane according
atomic
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21739688.6A
Other languages
English (en)
French (fr)
Inventor
Costana Mihaela IONICA BOUSQUET
Sylvain Petigny
Vincent Benoît RANIERI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Original Assignee
Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Centre de Recherche et dEtudes Europeen SAS filed Critical Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Publication of EP4179590A1 publication Critical patent/EP4179590A1/de
Pending legal-status Critical Current

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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6587—Influencing the atmosphere by vaporising a solid material, e.g. by using a burying of sacrificial powder
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/762—Cubic symmetry, e.g. beta-SiC
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/788—Aspect ratio of the grains
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/963—Surface properties, e.g. surface roughness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a solid electrolyte membrane made of an LLZO material, intended for a battery, in particular a lithium ion battery.
  • the invention also relates to such a battery.
  • the invention also relates to a method of manufacturing such a membrane.
  • Garnets of generic formula Li7La 3 ZnOi2 are conventionally called "lithium, lanthanum and zirconium oxide", or “LLZO", electroneutrality being ensured by the oxygen content, the phase of LLLasZnOii possibly being doped with a dopant M for the purpose of improving ionic conductivity and/or sinterability.
  • the dopant M can be in particular Al, P, Sb, Sc, Ti, V, Y, Nb, Hf, Ta, the lanthanides with the exception of La, Se, W, Bi, Si, Ge, Ga, Sn, Cr , Fe, Zn, Na, K, Rb, Cs, Fr, Mg, Ca, Sr, Ba or a mixture of these elements.
  • the LLZO comes in two crystallographic lattices:
  • a battery comprising a solid electrolyte membrane made of LLZO is known.
  • Such a membrane is manufactured by sintering and has a substantially planar shape, with a substantially constant thickness, typically around 400 microns. In this application, one seeks the highest possible ionic conductivity, and therefore as much cubic phase as possible.
  • the membrane can be isolated in an airtight container, under argon, which increases production costs.
  • the battery is at least partially assembled under air, and the degradation of the membrane in contact with the air can limit its performance.
  • An object of the invention is to satisfy, at least partially, this need.
  • this object is achieved by means of a molten solid electrolyte membrane having a thickness of less than 5 mm and intended for a lithium ion battery, the membrane being made of a polycrystalline product comprising less than 3.0% of amorphous phase and consisting, for more than 95% of its mass, of the elements Li, La, Zr, M and O, M being a dopant chosen from the group formed by Al, P, Sb, Sc, Ti, V, Y, Nb, Hf, Ta, lanthanides except La, Se, W, Bi, Si, Ge, Ga, Sn, Cr, Le, Zn, Na, K, Rb, Cs, Lr, Mg, Ca, Sr , Ba and mixtures thereof, the contents of said elements, measured after a decarbonation operation without loss of lithium, being defined by the formula Li a La b Zr c M d Oi2, in which the atomic indices are such that:
  • the resistance to aging in air of a fused membrane according to the invention is markedly greater than that of sintered membranes.
  • the manufacture of a molten polycrystalline product is a well-known technique.
  • the cooling conditions are only adapted so that the amount of amorphous phase is low.
  • the presence of a small quantity of amorphous phase makes it possible to control the ionic conductivity well. In particular, this conductivity does not vary significantly from one sample to another.
  • a membrane according to the invention further comprises one, and preferably several of the following optional characteristics: - at least one of the large faces of the membrane has a roughness Ra of less than 500 nm;
  • LLZO designating a lithium, lanthanum and zirconium oxide of generic formula LLLasZnOii;
  • the total quantity by mass of the cubic LLZO and quadratic LLZO phases is greater than 90.0%, preferably greater than 99.0%, in mass percentages based on the mass of the crystallized phases;
  • the cubic LLZO phase represents more than 35% of all the cubic LLZO and quadratic LLZO phases, in mass percentages;
  • a is greater than 2.800 and less than 8.300; and/or b is greater than 1.100 and less than 3.300; and/or c is greater than 0.600 and less than 1.900; and/or d is greater than 0.010 and less than 1.900;
  • a is greater than 4.500 and less than 8.000; and/or b is greater than 2.000 and less than 3.100; and/or c is greater than 1.000 and less than 1.900; and/or d is greater than 0.100 and less than 1.000;
  • a is greater than 6.000 and less than 7.000; and/or b is greater than 2.500 and less than 2.900; and/or c is greater than 1.400; and/or d is greater than 0.200 and less than 0.400;
  • the crystallized phases not containing lithium represent, in total, less than 3% of the mass of the crystallized phases
  • the polycrystalline product comprises less than 1.0% of amorphous phase and/or has a relative skeletal density greater than 90%; - the polycrystalline product has a microstructure composed for more than 90% by number of grains having an elongation factor greater than 2.5, called "elongated grains";
  • M includes element Y, the atomic index in element Y is greater than 0.005 and less than 0.300, and the sum of the atomic indices in elements M other than element Y is less than 0.300;
  • M includes the element Ce, and the atomic index of said element Ce is less than 0.300;
  • M includes the elements Ti and/or Fe, and the sum of the Ti and Fe atomic indices is less than 0.800;
  • M includes the element Al, the atomic number in element Al is greater than 0.005 and less than 1.300, and the sum of the atomic numbers in elements M other than aluminum is less than 0.300;
  • M includes the elements Ta and/or Nb and/or V, the sum of the atomic indices of Ta, Nb and V elements is greater than 0.010 and less than 1.000, and the sum of the atomic indices of M elements other than Ta elements, Nb and V is less than 0.300;
  • M includes the element Ta and the atomic number in element Ta is greater than 0.050 and less than 0.900, and the sum of the atomic numbers in elements M other than the element Ta is less than 0.300;
  • M includes the elements Sr and/or Ba and/or Ca and/or Mg, the sum of the atomic indices in elements Sr, B a, Ca and Mg is greater than 0.005, and the sum of the atomic indices in elements M other than the elements Sr, B a, Ca and Mg is less than 0.300;
  • M includes the elements Na and/or K, the sum of the atomic indices in elements Na and K is greater than 0.005, and the sum of the atomic indices in elements M other than the elements Na and K is less than 0.300;
  • M includes element Y, the atomic index in element Y is greater than 0.005 and less than 0.200, and the sum of the atomic indices in elements M other than element Y is less than 0.100;
  • M comprises the element Ce, and the atomic index of said element Ce is less than 0.200;
  • M includes the elements Ti and/or Fe, and the sum of the Ti and Fe atomic indices is less than 0.600;
  • M includes the element Al, the atomic number in element Al is greater than 0.150 and less than 0.700, and the sum of the atomic numbers in elements M other than aluminum is less than 0.100;
  • M includes the elements Ta and/or Nb and/or V, the sum of the atomic indices in elements Ta, Nb and V is greater than 0.300 and less than 0.700, and the sum of the atomic indices in elements M other than the elements Ta, Nb and V is less than 0.100;
  • M includes the elements Sr and/or Ba and/or Ca and/or Mg, the sum of the atomic indices in elements Sr, B a, Ca and Mg is greater than 0.100, and the sum of the atomic indices in elements M other than the elements Sr, B a, Ca and Mg is less than 0.100;
  • M includes the elements Na and/or K, the sum of the atomic indices in Na and K elements is greater than 0.100, and the sum of the atomic indices in M elements other than the Na and K elements is less than 0.100.
  • the invention also relates to a method for manufacturing a membrane according to the invention, said method comprising the following steps: a) mixing of raw materials so as to form a starting charge suitable for obtaining, at the end of the step c), a said polycrystalline product, b) melting of the starting charge until a liquid mass is obtained, c) cooling until complete solidification of said liquid mass, the cooling preferably being carried out at a higher speed at 200° C./s, d) polishing the polycrystalline product obtained at the end of step c) so as to obtain a molten membrane according to the invention.
  • step c) comprises the following steps: c1”) pouring the liquid mass, in the form of a jet, between two rollers; c2”) solidification by cooling the liquid mass cast in contact with the rollers until a block of polycrystalline product is obtained, at least partially solidified.
  • c1”) pouring the liquid mass, in the form of a jet, between two rollers
  • c2”) solidification by cooling the liquid mass cast in contact with the rollers until a block of polycrystalline product is obtained, at least partially solidified.
  • the invention finally relates to a lithium ion battery comprising a fused membrane according to the invention, preferably manufactured according to a method according to the invention, placed between an anode and a cathode of said battery.
  • molten membrane is used to refer to a membrane made of a material obtained directly by melting a starting charge, in the form of a liquid mass, then solidifying said liquid mass.
  • directly obtained it is meant that the material is obtained immediately after said solidification.
  • the melting is above 1200°C.
  • a membrane made of a sintered material is not a "molten membrane", even if the grains agglomerated by sintering are fused grains.
  • a “polycrystalline” material is called a solid material made up of a multitude of crystallites of varying size and orientation, as opposed to a single-crystal linen material made up of a single crystal.
  • the polycrystalline character of a material can for example be highlighted using observations made with a scanning electron microscope to highlight the grain boundaries and/or by Raman spectrometry. In the absence of special precautions, a molten product is polycrystalline.
  • the “relative skeletal density” of a product corresponds to the ratio equal to the skeletal density of said product divided by the absolute density of said product, expressed as a percentage.
  • “Skeletal density” of a product means the ratio equal to the mass of said product divided by the skeletal volume it occupies.
  • the skeletal volume of the product corresponds to the sum of the volumes of the material and of the closed pores, said skeletal volume being determined on a membrane or a plate by helium pycnometry.
  • absolute density of a product is meant the ratio equal to the mass of dry matter of said product after grinding to a fineness such that there remains substantially no closed porosity, divided by the volume of said mass of matter dry after grinding, said volume being able to be determined by helium pycnometry.
  • a "decarbonation without loss of lithium” operation is a classic operation during which a material is heated in such a way as to eliminate the carbonates without extract lithium.
  • the material can be heated under the conditions described in the examples.
  • the elements of the periodic table from atomic number 58 (cerium) to atomic number 71 (lutetium) are called "lanthanides”.
  • precursor of a compound or of an element is meant a constituent capable of supplying said compound or element, respectively, during the implementation of a manufacturing process according to the invention.
  • a solid electrolyte membrane according to the invention is intended for a lithium ion battery. Its dimensions are adapted for this purpose.
  • such a membrane has the general shape of a thin plate, of substantially constant thickness, and of which at least one of the two faces (or “large faces”), preferably both faces, are polished.
  • the thickness of the membrane is less than 5 mm, preferably less than 4 mm, preferably less than 3 mm, preferably less than 2 mm, preferably less than 1 mm, preferably less than 800 ⁇ m, preferably less than to 600 ⁇ m, preferably less than 400 ⁇ m, and/or preferably greater than 40 ⁇ m, preferably greater than 50 ⁇ m, preferably greater than 100 ⁇ m, preferably greater than 150 ⁇ m.
  • the thickness of the membrane is greater than 600 ⁇ m, preferably greater than 800 ⁇ m, or even greater than 1 mm.
  • the length and width are matched to the battery.
  • the length and/or the width is greater than 1 mm, preferably greater than 2 mm, preferably greater than 5 mm, or even greater than 10 mm, and/or preferably less than 300 mm, or even less than 200 mm, or even less than 100 mm.
  • the membrane may in particular have the shape of a rectangular plate or of a disc.
  • the roughness Ra of at least one of the large faces of the membrane is typically less than 500 nm, preferably less than 400 nm, preferably less than 300 nm, preferably less than 200 nm, preferably less than 100 nm, preferably less than 50 nm, preferably less than 40 nm, or even less than 30 nm.
  • LLZO membranes were made of a sintered material.
  • a membrane according to the invention is “melted”.
  • the membrane is therefore not an agglomerate of particles, but the result of shaping a block obtained by cooling a liquid mass.
  • the microstructure of the polycrystalline product which constitutes a membrane according to the invention is therefore specific.
  • the percentage of amorphous phase of the polycrystalline product is particularly low and cannot be precisely determined with conventional methods such as X-ray diffraction.
  • a surface percentage is evaluated, which can be measured as described in the examples.
  • the content of amorphous phase is less than 3.0%, less than 2.5%, preferably less than 2.0%, preferably less than 1.5%, preferably less 1.0%, or even less than 0.5%, or even substantially zero.
  • a low content of amorphous phase limits the variations in ionic conductivity from one sample to another of the polycrystalline product.
  • the total mass quantity of the oxides containing lithium, of the hydroxide phases containing lithium, and of the carbonate phases containing lithium is greater than 95.0%, preferably greater than 96.0%, preferably greater than 97, 0%, preferably greater than 98.0%, preferably greater than 99.0%.
  • the total mass quantity of the phases which are not oxides, hydroxides or carbonates containing lithium is preferably less than 5%, of preferably less than 4%, preferably less than 3%, preferably less than 2%, preferably less than 1%, in mass percentages based on the crystallized phases.
  • the total mass quantity of the cubic LLZO and quadratic LLZO phases is greater than 80.0%, preferably greater than 90.0%, preferably greater than 92.0%, preferably greater than 94.0%, of preferably greater than 95.0%, preferably greater than 96.0%, preferably greater than 97.0%, preferably greater than 98.0%, preferably greater than 99.0%, or even greater than 99.5 %, in mass percentages based on the mass of the crystallized phases.
  • the cubic LLZO phase represents more than 35%, preferably more than 40%, preferably more than 45%, preferably more than 50%, preferably more than 60%, preferably more than 70%, preferably more than 80%, preferably more than 90%, preferably more than 95% of all of the cubic LLZO and quadratic LLZO phases, in mass percentages.
  • the oxide phases containing lithium other than the LLZO phases, the hydroxide phases containing lithium, and the carbonate phases containing lithium together represent more than 95% of the crystallized phases containing lithium other than the LLZO phases.
  • the oxide phases containing lithium other than the LLZO phases, the hydroxide phases containing lithium, and the carbonate phases containing lithium are preferably chosen from LLO, LiOH, L12CO3 and their mixtures, preferably L12CO3.
  • the crystallized phases not containing lithium preferably represent, in total, less than 5%, preferably less than 3%, preferably less than 2%, preferably less than 1%, in mass percentages based on the crystallized phases .
  • the content and nature of the LLZO obtained depend in particular on the composition of the starting charge. The closer the chemical composition of the starting charge is to that of the desired LLZO, the greater the amount of said LLZO in the polycrystalline product.
  • the polycrystalline product has a microstructure composed for more than 90% by number of grains having an elongation factor of less than 1.6, preferably less than 1.4, preferably less than 1.25, even less than 1.20, the elongation factor being equal to the ratio of the largest dimension of the grain on the smallest dimension of said grain, measured perpendicular to the largest dimension of the grain, on a cross-sectional view of the polycrystalline product.
  • the grains of the product have a preferred orientation, the cut is made parallel to said preferred direction. In particular, when the liquid mass of molten material has been cooled by contact with a cold plate, the cut must be made perpendicular to said plate.
  • the preferred orientation of the grains is the direction of the length of the majority of the grains.
  • the polycrystalline product has an average grain size greater than 10 ⁇ m, preferably greater than 20 ⁇ m, preferably greater than 30 ⁇ m, preferably greater than 40 ⁇ m, preferably greater than 50 ⁇ m, or even greater than 60 ⁇ m , or even greater than 70 ⁇ m, and/or preferably less than 500 ⁇ m, preferably less than 450 ⁇ m, preferably less than 400 ⁇ m, preferably less than 350 ⁇ m, preferably less than 300 ⁇ m, or even less than 250 ⁇ m , said mean size being measured by a “Mean Linear Intercept” method. A measurement method of this type is described in standard ASTM E1382.
  • the polycrystalline product has a microstructure composed for more than 10%, even for more than 20%, even for more than 30%, even for more than 40%, even for more than 50%, even for more of 60%, even for more than 70%, even for more than 80%, even for more than 90%, even for more than 95%, even for more than 99% in number, of elongated grains, preferably having a factor elongation greater than 3, or even greater than 4, or even greater than 5.
  • - a is greater than 2.800, preferably greater than 3.000, preferably greater than
  • - b is greater than 1.100, preferably greater than 1.200, preferably greater than 1.300, or even greater than 1,500, or greater than 1,800, or greater than 2,000, or greater than 2,200, or greater than 2,400, or greater than 2,500, and /Where less than 3.300, preferably less than 3.100, preferably less than 3.000, preferably less than 2.900; and or
  • - c is greater than 0.600, preferably greater than 0.700, preferably greater than 0.800, or even greater than 0.900, or greater than 1.000, or greater than 1.200, or greater than 1.400 and/or less than 1.900; and or
  • - d is greater than 0.010, preferably greater than 0.050, or even greater than 0.100, or even greater than 0.200, and/or less than 1.900, preferably less than 1.800, preferably less than 1.700, preferably less than 1.500, preferably less than 1.300, preferably less than 1.200, preferably less than 1.100, preferably less than 1.000, preferably less than 0.900, preferably less than 0.800, preferably less than 0.700, preferably less than 0.600, or even less than 0.500 , or even less than 0.400.
  • the composition of the polycrystalline product respects several of the preferred conditions above relating to the atomic indices a, b, c and d.
  • M can be introduced into the starting charge to be melted as traces in a raw material.
  • the atomic index d takes these additions into account.
  • M is preferably selected from the group formed by Al, Sb, V, Y, Nb, Hf, Ta, Ce, Si, Na, K, Mg, Ca, Sr, Ba and mixtures thereof, preferably from the group formed by Al, V, Y, Nb, Hf, Ta, Si, Na, Mg, Ca, Sr and mixtures thereof.
  • M comprises the element Y, the atomic index of said element Y being less than 0.300, preferably less than 0.200 and greater than 0.005, preferably greater than 0.010.
  • M comprises the element Ce, the atomic index of said element Ce being less than 0.800, preferably less than 0.600, preferably less than 0.400, preferably less than 0.300, or even less than 0.200 and /or greater than 0.005, preferably greater than 0.010, or even greater than 0.050, or even greater than 0.100.
  • M comprises Ti and/or Fe, the sum of the atomic indices in Ti and/or Fe being less than 0.800, preferably less than 0.700, preferably less than 0.600 and/or greater than 0.005, preferably greater than 0.010, or even greater than 0.050, or even greater than 0.100, or even greater than 0.200, or even greater than 0.300.
  • the polycrystalline product is such that: - the atomic index in element Al is greater than 0.005, preferably greater than 0.010, preferably greater than 0.050, preferably greater than 0.100, preferably greater than 0.150, and/or, preferably less than 1.300, preferably less than 1.200, preferably less than 1.100, preferably less than 1.000, preferably less than 0.900, preferably less than 0.800, preferably less than 0.700, preferably less than 0.600, and
  • the sum of the atomic indices in elements M other than aluminum is less than 0.300, preferably less than 0.200, preferably less than 0.100.
  • the polycrystalline product is such that:
  • the sum of the atomic indices in elements tantalum, niobium and vanadium is greater than 0.010, preferably greater than 0.050, or even greater than 0.100, or even greater than 0.200, or even greater than 0.300 and/or, preferably, less than 1.000, of preferably less than 0.900, preferably less than 0.800, preferably less than 0.700, and
  • the sum of the atomic indices in elements M other than the elements tantalum, niobium and vanadium is less than 0.300, preferably less than 0.200, preferably less than 0.100.
  • the polycrystalline product is such that:
  • the tantalum atomic index is greater than 0.010, preferably greater than 0.050, or even greater than 0.100, or greater than 0.200, or greater than 0.300 and/or, preferably, less than 1.000, preferably less than 0.900, preferably less than 0.800, preferably less than 0.700, and
  • the sum of the atomic indices in elements M other than the tantalum element is less than 0.300, preferably less than 0.200, preferably less than 0.100.
  • the polycrystalline product is such that:
  • the atomic index of yttrium element is greater than 0.005, preferably greater than 0.010 and/or, preferably less than 0.300, preferably less than 0.200, and
  • the polycrystalline product is such that:
  • the sum of the atomic indices in the elements strontium, barium, calcium and magnesium is greater than 0.005, preferably greater than 0.010, preferably greater than 0.050, or even greater than 0.100 and/or preferably less than 1.500, preferably less than 1.300 , preferably less than 1.000, and
  • the sum of the atomic indices in elements M other than the elements strontium, barium, calcium and magnesium is less than 0.300, preferably less than 0.200, preferably less than 0.100.
  • the polycrystalline product is such that:
  • the sum of the atomic indices in the elements sodium and potassium is greater than 0.005, preferably greater than 0.010, preferably greater than 0.050, preferably greater than 0.100 and/or, preferably less than 1.500, preferably less than 1.300, preferably less than 1,000, and
  • the sum of the atomic indices in elements M other than the elements sodium and potassium is less than 0.300, preferably less than 0.200, preferably less than 0.100.
  • the quantity by mass of elements other than Li, La, Zr, M and O is less than 4.0%, preferably less than 3.0%, preferably less than 2.0%, preferably less than 1 .5%, preferably less than 1.0%, preferably less than 0.5%.
  • the elements other than Li, La, Zr, M and O are unavoidable constituents, introduced involuntarily and necessarily with the raw materials.
  • the relative skeletal density of the polycrystalline product is preferably greater than 85%, preferably greater than 88%, preferably greater than 90%, preferably greater than 92%, preferably greater than 94%, preferably greater than 95% , preferably greater than 96%, preferably greater than 97%, preferably greater than 98%, preferably greater than 98.5%, preferably greater than 99%, preferably greater than 99.5%, preferably greater at 99.8%.
  • the ionic conductivity is improved thereby.
  • the invention also relates to a manufacturing method comprising steps a) to d).
  • a method according to the invention makes it possible to obtain high relative densities.
  • it avoids a step of forming a powder, then sintering.
  • a starting charge for manufacturing a membrane according to the invention is formed from compounds of lithium, lanthanum, zirconium and optionally element M, in particular in the form of oxides and/or carbonates and/or hydroxides and/or oxalates and/or nitrates, and/or precursors of the elements lithium, lanthanum, zirconium and M.
  • the composition of the starting charge can be adjusted by addition of pure oxides or mixtures of oxides and/or precursors, in particular LEO, L12CO3, LiOH, La203, ZrCE, a lanthanum carbonate, a zirconium hydrate, oxide(s) of the element M , carbonate(s) of the element M, hydroxide(s) of the element M.
  • the use of oxides and/or carbonates and/or hydroxides and/or nitrates and/or of oxalates improves the availability of oxygen necessary for the formation of phase Li a LabZr c MdOi2 and its electroneutrality, and is therefore preferred.
  • At least one, or even all of the lanthanum, zirconium and M elements are introduced into the starting charge in the form of oxides.
  • oxide powders are used to provide the lanthanum, zirconium and M elements, and a carbonate powder to provide the lithium element.
  • the compounds providing the elements lithium, lanthanum, zirconium and M are chosen from L12CO3, L12O, LiOH, La2Ü 3 , ZrÜ2, the carbonates of the element M, the hydroxides of the element M, and the oxides of the m element.
  • the compounds providing the elements lithium, lanthanum, zirconium and M together represent more than 90%, preferably more than 99%, in mass percentages, of the constituents of the starting charge.
  • these compounds represent, together with the impurities, 100% of the constituents of the starting charge.
  • no compound other than those providing the elements lithium, lanthanum, zirconium and M, or even any compound other than L12CO3, L12O, LiOH, La20 3 , ZrO2, the carbonates of the element M, the hydroxides of the element M , and the oxides of the element M are not deliberately introduced into the starting charge.
  • the sum of L12CO3, L12O, LiOH, La2O 3 , ZrO2, the carbonates of element M, the hydroxides of element M, and the oxides of element M represents more than 99% by mass of the starting charge.
  • the quantities of lithium, lanthanum, zirconium and element M of the starting charge are essentially found in the polycrystalline product produced.
  • the person skilled in the art knows how to adapt the quantity of these elements in the starting charge according to the content he wishes to find in the molten products and the melting conditions. implemented.
  • the particle sizes of the powders used can be those commonly encountered in melting processes.
  • Intimate mixing of the raw materials can be carried out in a mixer. This mixture is then poured into a melting furnace.
  • step b) the starting charge is melted.
  • All known furnaces are possible, such as an induction furnace, a plasma furnace or other types of Héroult furnace, provided that they allow the starting charge to be completely melted. Melting in a crucible in a heat treatment furnace, preferably in an electric furnace, preferably in an oxygenated environment, for example under air, is also possible. Electrofusion advantageously allows the manufacture of large quantities of polycrystalline product with interesting yields.
  • the energy supplied is preferably greater than 1100 kWh/T of starting load, preferably greater than 1200 kWh/T.
  • the energy supplied is between 1200 kWh/T and 1800 kWh/T, preferably between 1300 kWh/T and 1600 kWh/T.
  • the voltage is for example 130 volts and the power 200 kW.
  • An induction furnace can also advantageously be implemented.
  • the starting charge is in the form of a liquid mass, which may optionally contain a few solid particles, but in an insufficient quantity for them to be able to structure said mass.
  • a liquid mass must be contained in a container.
  • the general environment of the liquid mass can be neutral, reducing or oxidizing, preferably oxidizing, preferably being air.
  • the temperature of the molten liquid is preferably higher than the melting temperature of the polycrystalline product, preferably higher than 1200° C., or even higher than 1250 °C, or even above 1300°C and preferably below 1650°C, preferably below 1600°C, preferably below 1550°C, preferably below 1500°C.
  • the cooling rate is preferably greater than 50°C/s, preferably greater than 100°C/s, preferably greater than 200°C/s.
  • the cooling rate is greater than 200°C/s and preferably less than 10,000°C/s, preferably less than 1000°C/s, preferably less than 800°C/s. s, preferably less than 600° C./s.
  • a high cooling rate makes it possible to increase the mass quantity of cubic LLZO phase, on the basis of the mass of the crystallized phases.
  • a high cooling rate also makes it possible, advantageously, to reduce the amount of amorphous phase.
  • a high cooling rate finally makes it possible to create a temperature gradient making it possible to create a microstructure having a large quantity of elongated grains, oriented in the direction of the greatest temperature gradient.
  • cooling by contact with a cooled plate makes it possible to orient the elongated grains substantially perpendicular to the plate.
  • the anisotropy may decrease as the region under consideration is further away from the cooled plate.
  • the anisotropy results from the passage of the liquid mass between two rollers which are themselves cooled.
  • step c) comprises the following steps: c') pouring the liquid mass into a mould; c2′) solidification by cooling of the liquid mass cast in the mold until an at least partially solidified block is obtained; c3') demoulding of the block.
  • step c1′ the liquid mass is poured into a mold capable of withstanding the bath of molten liquid.
  • a mold capable of withstanding the bath of molten liquid.
  • graphite or cast iron molds are used. Molds are also described in US 3,993,119.
  • the coil is considered to constitute a mould. Casting is preferably carried out under air.
  • step c2′ the liquid mass poured into the mold is cooled until an at least partially solidified block is obtained.
  • a mold of the type of those described in US Pat. No. 3,993,119 advantageously makes it possible to obtain a high mass quantity of cubic LLZO phase, on the basis of the mass of the crystallized phases.
  • the block is unmolded.
  • the block is removed from the mold as soon as it has sufficient rigidity to substantially retain its shape.
  • step c1′) and/or in step c2′) and/or after step c3′ said liquid mass in the process of solidification is brought into contact, directly or indirectly, with a fluid oxygenated, preferably comprising more than 20% by volume of oxygen, preferably a gas, preferably air.
  • a fluid oxygenated preferably comprising more than 20% by volume of oxygen, preferably a gas, preferably air.
  • This bringing into contact can be carried out as soon as casting takes place.
  • step c3′ To facilitate bringing the liquid mass into contact with the oxygenated fluid, it is preferable to unmold the block as quickly as possible, if possible before complete solidification, and then to immediately begin bringing it into contact with the oxygenated fluid. Solidification then continues in step c3′).
  • contact with the oxygenated fluid is maintained until the complete solidification of the block.
  • a block is obtained capable of giving, after step d), a membrane whose thickness is less than 5 mm, preferably less than 4 mm, preferably less than 3 mm, preferably less than 2 mm, preferably less than 1 mm, preferably less than 800 ⁇ m, preferably less than 600 ⁇ m, preferably less than 400 ⁇ m, and preferably greater than 40 ⁇ m, preferably greater than 50 ⁇ m, preferably greater than 100 pm, preferably greater than 150 pm.
  • step c) comprises the following steps: c1”) pouring the liquid mass, in the form of a jet, between two rolls, preferably both rotating and/or cooled; c2”) solidification by cooling the liquid mass cast in contact with the rollers until an at least partially solidified block is obtained.
  • step c1”) the liquid mass is poured in the form of a jet between two rollers capable of resisting the molten liquid, so as to laminate the jet of molten liquid.
  • the rollers are made of steel.
  • they are driven by opposite rotational movements, so as to laminate the jet of liquid.
  • said rollers are cooled, preferably using a circulation of fluid, preferably a liquid, preferably water, preferably without said liquid being in contact with the jet of molten liquid.
  • step c2 the jet of liquid flowing between the rollers is cooled until an at least partially solidified block is obtained.
  • the use of such a process advantageously makes it possible to obtain, after complete solidification, a plate having a high relative skeletal density and of low thickness, which, after step d), makes it possible to obtain a membrane suitable for a battery to lithium ions.
  • step c1”) and/or in step c2”) said liquid mass in the process of solidification is brought into contact, directly or indirectly, with an oxygenated fluid, preferably comprising more than 20% in volume of oxygen, preferably a gas, preferably air.
  • an oxygenated fluid preferably comprising more than 20% in volume of oxygen, preferably a gas, preferably air.
  • contact with the oxygenated fluid is maintained until the complete solidification of the block.
  • the elements Li, La, Zr, M and O combine in the form of cubic LLZO phase, quadratic LLZO phase, or even other phases containing lithium, (and in particular other oxide phases containing lithium, hydroxide phases containing lithium, and carbonate phases containing lithium) and/or phases not containing lithium.
  • step d) the polycrystalline product obtained at the end of step c) is polished so as to reduce its roughness.
  • the polishing is carried out on at least one, preferably each of the two large faces of the membrane.
  • the roughness Ra of at least one of the large faces of the membrane, preferably of each of the two large faces of the membrane is less than 500 nm, preferably less than 400 nm, preferably less than 300 nm, preferably less than 200 nm, preferably less than 100 nm, preferably less than 50 nm, preferably less than 40 nm, or even less than 30 nm.
  • step d) the thickness of the polycrystalline product obtained at the end of step c) is reduced, preferably until a thickness of less than 5 mm is obtained, preferably less than 4 mm, preferably less than 3 mm, preferably less than 2 mm, preferably less than 1 mm, preferably less than 800 ⁇ m, preferably less than 600 ⁇ m, preferably less than 400 ⁇ m, and preferably greater than 40 ⁇ m, preferably greater than 50 ⁇ m, preferably greater than 100 ⁇ m, preferably greater than 150 ⁇ m.
  • the reduction may result totally or partially from the polishing operation.
  • the thickness of the polycrystalline product is limited from the melting, in particular during a step cl”).
  • machining makes it possible to reduce the length and/or the width of the polycrystalline product obtained at the end of step c).
  • the final length of the membrane obtained is preferably greater than 1 mm and less than 300 mm, typically between 10 mm and 100 mm.
  • the final width of the membrane is preferably greater than 1 mm and less than 300 mm, typically between 10 mm and 100 mm.
  • the polycrystalline product and/or the membrane are cut in such a way as to retain only regions having a high quantity of elongated grains.
  • the membrane is dried, preferably at a temperature above 90° C., preferably above 100° C., and/or preferably less than 200° C., preferably less than 150° C., the holding time at this temperature being preferably greater than 5 hours, preferably greater than 10 hours, preferably greater than 20 hours, or even greater than 50 hours and / or preferably less than 200 hours, preferably less than 100 hours.
  • the chemical analysis is determined using the following method:
  • the samples are preferably stored under vacuum or in a neutral atmosphere, for example under argon, in order to avoid carbonation.
  • the samples to be characterized are then dry ground in an RS 100 grinder marketed by the Retsch company, equipped with a bowl and a tungsten carbide roller, so as to have a maximum size of less than 160 ⁇ m (this is that is to say that more than 99.5% by mass of the particles of the ground powder have a size of less than 160 microns).
  • the carbon content of the powder obtained is determined by instrumental gas analysis (or "Instrumental gas analysis"), for example on a carbon / sulfur analyzer EMIA-820V from HORIBA Scientific.
  • carbon content is less than 0.3%, dissolution by hydrochloric acid attack is carried out and the content of the various elements is determined by inductively coupled plasma spectrometry or ICP-AES.
  • the powder is placed in a magnesia crucible.
  • the crucible is placed in an electric furnace then raised to 950° C. and maintained at this temperature for 15 minutes. After cooling, the heat-treated powder is brought into solution by attacking with hydrochloric acid and the content of the various elements is determined by inductively coupled plasma spectrometry or ICP-AES.
  • the samples to be characterized are ground dry in an RS 100 grinder marketed by the company Retsch, equipped with a bowl and a tungsten carbide roller, so that they are in the form of a powder. exhibiting a refusal at 40 ⁇ m of less than 5% by mass.
  • the acquisitions are carried out using a device of the D8 Endeavor type from the company Bruker, over an angular range 2Q between 5° and 80°, with a step of 0.01°, and a counting time of 0.68 s/step.
  • the front optic has a 0.3° primary slit and a 2.5° Soller slit.
  • the sample is rotating on itself at a speed equal to 15 rpm, with use of the automatic knife.
  • the rear optics have a 2.5° Soller slit, a 0.0125 mm nickel filter and a 1D detector with an aperture equal to 4°.
  • the diffraction patterns are then qualitatively analyzed using EVA software and the ICDD2016 database.
  • File 182312 of the ICSD database makes it possible to identify the cubic LLLasZnOii phase and file 246816 of the ICSD database makes it possible to identify the quadratic LÎ7La 3 Zr20i2 phase.
  • the highlighted phases may show a slight shift in peaks compared to the data sheets used.
  • the quadratic LLZO phase optionally doped, is generally less distorted than the quadratic LÎ7La 3 Zr20i2 phase of the ICSD database file, and the characteristic peaks of said phase can be positioned at greater 2Q diffraction angles. lower than those indicated in the ICSD database sheet.
  • secondary phases are preferably crystallized phases of the group formed by orthorhombic La2Zr207 (ICDD sheet -01-070-5602), orthorhombic LiLa02 (ICDD sheet 00-019-0722), monoclinic LLZKL (ICDD sheet 01-01- 070-8744), monoclinic L12CO3 (ICDD sheet 01-087-0728), hexagonal La20 3 (ICDD sheet 01-071-5408), monoclinic Z1 ⁇ 2 (ICDD sheet 00-37-1484), and mixtures thereof.
  • orthorhombic La2Zr207 ICDD sheet -01-070-5602
  • orthorhombic LiLa02 ICDD sheet 00-019-0722
  • monoclinic LLZKL ICDD sheet 01-01- 070-8744
  • monoclinic L12CO3 ICDD sheet 01-087-0728
  • hexagonal La20 3 ICDD sheet 01-071-5408
  • monoclinic Z1 ⁇ 2 ICDD sheet 00-37-1484
  • the measurement of the mass quantity of the cubic and quadratic LLZO phases as well as the other crystallized phases is carried out by Rietveld refinement using the HighScore Plus software.
  • profile base width is at least equal to 20.
  • the Rietveld refinement must be carried out in manual mode according to the following strategy, the transition from one step to the next only taking place after ensuring that the refinement has converged:
  • the surface percentage of amorphous phase is determined by the following method:
  • Three samples, each of dimensions substantially equal to 50 mm x 15 mm x 2 mm are taken without using water, for example using a hammer, in the sample.
  • Each sample is then glued in a sample holder and then undergoes polishing, in order to obtain a good surface condition, said polishing being carried out at least with a grade 220 paper used with an alcohol-based lubricant, then with using diamond suspensions in a mixture of polyethylene glycol and polypropylene glycol.
  • the surface obtained is then cleaned with pure isopropanol.
  • the polished surface obtained is the surface that will be analyzed by Raman imaging.
  • thermoelectric module EMCCD camera or "Electron Multiplying Charge Coupled Device”, with a resolution equal to 1600 x 200 pixels, cooled by the Peltier effect thanks to a thermoelectric module,
  • Each image is reconstructed point by point. Each point corresponds to a Raman spectrum.
  • Each phase whether crystallized or amorphous, has a unique spectral signature.
  • the distribution of the phases present can be viewed by assigning a color code to each phase, i.e. to each type of spectrum obtained.
  • the crystallized phases identified by X-ray diffraction are first identified. Then, in a second step, the unassigned zones are analyzed so as to determine whether they consist of crystallized phases or of amorphous phases.
  • the image obtained represents the distribution of the different crystallized and amorphous phases present.
  • the amorphous phase area is calculated in pixels, as well as the total area of the image.
  • the surface percentage of amorphous phase of the product is equal to the sum of the surfaces of the zones of amorphous phases of each image divided by the sum of the total surfaces of the images, expressed as a percentage.
  • the average grain size was measured by the “Mean Linear Intercept” method.
  • a method of this type is described in standard ASTM E1382. According to this standard, lines of analysis are traced on images of the polycrystalline product, then, along each line of analysis, the lengths, called “intercepts”, are measured between two consecutive grain boundaries intersecting said line of analysis.
  • the intercepts were measured on images, obtained by scanning electron microscopy, of samples of molten polycrystalline products, said sections having previously been coated in a resin and polished until obtaining a mirror quality , said polishing being carried out at least with a grade 220 paper used with an alcohol-based lubricant, then using diamond suspensions in a mixture of polyethylene glycol and polypropylene glycol, the surface obtained then being cleaned with using pure isopropanol.
  • the magnification used for taking the images is chosen so as to visualize approximately 40 grains on an image. 5 images per polycrystalline product were produced.
  • Roughness is measured using a Mitutoyo Surftest SJ-210 roughness tester, model 178-560-01D, equipped with a 178-296 probe, used with:
  • Air aging is measured as follows:
  • the membranes are then examined with the naked eye to assess their physical integrity.
  • the following examples are provided for illustrative purposes and do not limit the invention.
  • the fused membranes were fabricated as follows.
  • a powder comprising more than 99.4% by mass of lithium carbonate L12CO3, the median size of which is equal to 26 ⁇ m, and comprising traces of the elements Na, Mg and Ca;
  • a powder comprising more than 99.4% by mass of lanthanum oxide La20 3 , the median size of which is less than 10 ⁇ m, and comprising traces of the elements Y, Fe, Ca , Si and Ti;
  • a CC10 zirconia powder marketed by the European Society of Refractory Products, comprising more than 98.5% by mass of Z1 ⁇ 2 and, in trace amounts, the elements Al, Si, Na, Hf, Fe, Ca, Mg and Ti;
  • a powder comprising more than 99.8% by mass of Ta2Ü5, the maximum particle size of which is less than 10 ⁇ m, and comprising in particular the trace elements of the elements Fe, Al, Si, Ca, Mg and Ti.
  • the elements Al and/or Ca and/or Fe and/or Hf and/or Mg and/or Na and/or Si and/or Ti and/or Ta and/or Y result from the presence of these elements, in trace amounts, in the raw materials used.
  • the starting charge is defined in the following table 1, in mass percentages:
  • the starting charge of a mass of 25 kg was poured into a Héroult-type arc melting furnace. It was then melted with a voltage of 130 Volts and an applied energy substantially equal to 1500 kWh/T, in order to melt the entire mixture completely and homogeneously.
  • the mass of molten liquid was poured in the form of a jet between two rolls of diameter equal to 800 mm, in steel cooled using a circulation of water so that their surface temperature is equal to 16°C, with opposite rotational movements, at a speed equal to 5 rpm, and separated from each other by an equal distance to 2.5 mm, so as to entrain and laminate the jet between said rollers.
  • the temperature of the jet of molten liquid was between 1300°C and 1450°C.
  • Tables 2 and 3 below provide the chemical composition and the crystallographic composition of these plates. Polishing the plates as described below does not alter these results.
  • the surface percentage of amorphous phase in each of the examples was measured below 3%.
  • polishing is carried out on each of the two large faces so as to obtain a fused membrane with a thickness equal to 1.5 mm and having a roughness Ra, measured on each of the two large faces, of less than 100 n.
  • each powder is then shaped by uniaxial pressing, so as to obtain a pellet having a diameter equal to 13 mm and a mass substantially equal to 1 g under the following pressing conditions:
  • Each pellet is then placed on an MgO plate, said MgO plate being placed on a bed of L12CO3 powder disposed in a first alumina gazette.
  • a second alumina gazette is then placed upside down on the first alumina gazette.
  • the assembly is then introduced into an electric furnace, so as to sinter each pellet, under air and at atmospheric pressure in the following thermal cycle:
  • Each sintered pellet obtained has a thickness equal to 1.5 mm.
  • This stability of the membranes according to the invention is considered as a signature of the fusion process. In other words, it reflects the fact that these membranes were obtained directly by fusion.
  • a membrane according to the invention having a relative skeletal density of less than 90% exhibits less aging than a sintered reference membrane of the same relative skeletal density.
  • a fused membrane according to the invention exhibits less aging in air than a sintered reference membrane.
  • the inventors have also observed that a limited variation in the relative skeletal density of the fused membranes according to the invention does not substantially modify their resistance to ageing.
  • the method according to the invention allows the membranes to be stored, manufactured and used in air, which considerably reduces the costs and widens the spectrum of possible applications.
  • Lower air aging also makes it possible to limit the resistance at the interfaces and therefore to maintain a high ionic conductivity when the battery is assembled in air.
  • the material which constitutes a membrane according to the invention is preferably the result of the solidification of an entirely liquid liquid mass before being cooled in order to be solidified. Its manufacturing process is then very simple since it suffices to melt the raw materials, preferably in the form of powders, then, after obtaining a bath of molten liquid, to solidify this bath to obtain a block under the shape of the membrane or from which it is possible to extract the membrane.
  • the present invention is not limited to the embodiments described provided by way of illustrative and non-limiting examples.
  • the membranes according to the invention are not limited to particular shapes or dimensions.
EP21739688.6A 2020-07-09 2021-07-06 Membran aus einem polykristallinen llzo-produkt Pending EP4179590A1 (de)

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FR2007268A FR3112431B1 (fr) 2020-07-09 2020-07-09 Membrane en un produit polycristallin de llzo
PCT/EP2021/068688 WO2022008522A1 (fr) 2020-07-09 2021-07-06 Membrane en un produit polycristallin de llzo

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US3993119A (en) 1974-11-08 1976-11-23 Norton Company Progressively or continuously cycled mold for forming and discharging a fine crystalline material
JP6260250B2 (ja) * 2012-12-29 2018-01-17 株式会社村田製作所 固体電解質用材料
JP6028694B2 (ja) * 2013-08-23 2016-11-16 株式会社豊田中央研究所 ガーネット型イオン伝導性酸化物の製造方法及び複合体の製造方法
CN107074583B (zh) * 2014-10-27 2019-06-28 国立研究开发法人产业技术综合研究所 含锂石榴子石晶体和全固体锂离子二次电池
KR101745930B1 (ko) * 2015-10-06 2017-06-12 한국생산기술연구원 복합공정에 의한 전고체 리튬이차전지용 고체전해질의 제조방법 및 그를 포함하는 전고체 리튬이차전지의 제조방법
KR102137801B1 (ko) * 2016-05-26 2020-07-24 내셔날 인스티튜트 오브 어드밴스드 인더스트리얼 사이언스 앤드 테크놀로지 저대칭 가닛 관련형 구조 고체 전해질 및 리튬 이온 이차 전지
EP3494613A4 (de) * 2016-08-05 2020-03-11 QuantumScape Corporation Durchscheinende und transparente separatoren
US11053134B2 (en) * 2017-08-25 2021-07-06 Arizona Board Of Regents On Behalf Of Arizona State University Synthesis of nanosized cubic lithium lanthanum zirconate fast ion conductor
CN111326787A (zh) * 2020-02-19 2020-06-23 北京化工大学 一种石榴石结构的混合离子-电子导体及其在储能器件中的应用

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FR3112431A1 (fr) 2022-01-14
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