Metal-substituted lithium-rich halide solid electrolyte

Abstract

The present invention relates to metal-substituted lithium-rich solid electrolytes, methods for producing said solid electrolytes, and batteries containing said solid electrolytes. These solid electrolytes exhibit increased ionic conductivity. Furthermore, batteries containing the solid electrolytes according to the present invention have optimized capacity.

Description

[Technical Field]

[0001] The present invention relates to a metal-substituted lithium-rich solid electrolyte material, a method for producing said solid electrolyte, and a battery containing said solid electrolyte. [Background technology]

[0002] The rapid development of small and lightweight electronic products, electronic devices, communication devices, and the like, and the widespread need for electric vehicles due to environmental concerns, have led to a demand for improved performance of secondary batteries used as power sources for these products. Among these, lithium secondary batteries have come into the spotlight as high-performance batteries due to their high energy density and high reference electrode potential.

[0003] However, the electrolytes conventionally used in lithium secondary batteries are liquid electrolytes such as organic solvents, which can lead to continuous safety issues such as electrolyte leakage and fire risks.

[0004] Recently, solid-state batteries, which contain solid electrolytes rather than liquid electrolytes, have been used to improve the safety characteristics of lithium secondary batteries and have attracted much attention. For example, solid electrolytes are typically safer than liquid electrolytes due to their non-flammable or flame-retardant properties.

[0005] To improve safety, sulfur-free solid electrolytes have been developed, which avoid the formation of hydrogen sulfide when exposed to the atmosphere. Furthermore, lithium halide solid electrolytes exhibit high ionic conductivity and oxidative stability.

[0006] Wang et al (Nature Communications 2021, 12, 4410) describe the synthesis of Li2ZrCl6 and a battery containing Li2ZrCl6 as the cathode, anode, and solid electrolyte.

[0007] WO 2021 / 161604 is Li2.5 Zr 0.5 Al 0.5 F6, and Li 2.6 Zr 0.4 Al 0.6 It is intended to synthesize an aluminum-substituted fluoride-based solid electrolyte such as F6.

Summary of the Invention

Problems to be Solved by the Invention

[0008] An object of the present invention is to provide a metal-substituted lithium-rich halide-based solid electrolyte.

[0009] A further object of the present invention is to provide a method for manufacturing the solid electrolyte.

[0010] A further object of the present invention is to provide a battery including the solid electrolyte.

Means for Solving the Problems

[0011] In a first aspect, the object of the present invention is achieved by providing a solid electrolyte having a composition according to formula (I):

[0012] Li 2+a Al a Zr 1-a X6 (I)

[0013] Where 0 < a < 1, and X is selected from the group consisting of Cl, Br, I, and any combination of the group consisting of F, Cl, Br, and I. In a preferred embodiment, the solid electrolyte is according to the present invention, where 0.2 < a < 0.3, or 0.3 < a < 1.0.

[0014] <00系列の番号を変えることはできません。 The inventors have surprisingly found that these aluminum-substituted lithium-rich zirconium-based and halide-based solid electrolyte compositions exhibit an increase in ionic conductivity, as shown in the attached examples.

[0015] To overcome the safety concerns due to the presence of sulfur in solid electrolyte compositions, the inventors explored halide-based solid electrolytes because they are ionically conductive, easily deformable, and have high oxidative stability.

[0016] In a further aspect, the present invention provides a method for producing said solid electrolyte.

[0017] In a further aspect, the present invention provides a battery comprising a solid electrolyte according to the present invention.

[0018] The inventors have surprisingly found that batteries comprising the solid electrolyte according to the invention have increased capacity compared to batteries comprising LiZrCl as the solid electrolyte, particularly when using a bilayer separator comprising the solid electrolyte of the invention and a sulfide solid electrolyte of the defined composition.

[0019] Without wishing to be bound by any theory, the inventors believe that the presence of the double layer limits side reactions occurring within the battery, and in particular avoids reactions between the sulfide electrolyte and the cathode, and in particular the solid electrolyte contained within the cathode. [Brief explanation of the drawings]

[0020] [Figure 1] Figure 1 shows the X-ray diffraction patterns of CEX1, EX1, EX3-4, and EX6. [Figure 2] Figure 2 shows cells 1-4 cycled at C / 20 from 1.9V to 3.7V vs. Li / In. DETAILED DESCRIPTION OF THE INVENTION

[0021] The drawings and the following detailed description set forth in detail preferred embodiments for enabling the present invention to be practiced. While the present invention has been described with reference to these specific preferred embodiments, it will be understood that the present invention is not limited to these preferred embodiments. On the contrary, the present invention encompasses numerous alternatives, modifications, and equivalents which will become apparent in light of the following detailed description and the accompanying drawings.

[0022] When used in the present specification and claims, the term "comprises" should not be interpreted as being limited to the means listed below, nor does it exclude other elements or steps. It should be interpreted as specifying the presence of the mentioned or stated features, integers, steps, or components, but does not preclude the presence or addition of one or more other features, integers, steps, or components, or groups thereof. Thus, the scope of the expression "a composition comprising components A and B" should not be limited to a composition consisting only of components A and B. This means that, in the context of the present invention, the only relevant components of the composition are A and B. Thus, the terms "comprises" and "comprises" encompass the more restrictive terms "consisting essentially of" and "consisting of."

[0023] As used herein, the term "solid-state battery" refers to a cell or battery that contains only solid or substantially solid components, such as solid electrodes (e.g., anode and cathode) and a solid electrolyte.

[0024] As referred to herein, X-ray diffraction (XRD) is measured using Cu-Kα radiation (λ Cu = 1.5418 Å). Preferably, sample preparation is performed in an Ar-filled glove box, where the sample is placed in an airtight sample holder capped with a Be window.

[0025] As referred to herein, electrochemical impedance spectroscopy measurements were performed using a frequency response analyzer (MTZ-35, Biologic) and an intermediate temperature system (ITS, Biologic). Preferably, the powder was pelletized between two carbon papers using a 6 mm diameter die in a uniaxial hydraulic press (approximately 1.5 tons). The pellets were loaded into an airtight sample holder (CESH, Biologic) in an Ar-filled glove box and measured at temperatures ranging from 25 to 75°C. A frequency range of 35 MHz to 1 Hz and an applied voltage of 50 mV were preferably used. Ionic conductivity was determined by extracting the resistance from the Nyquist plot and calculating the conductivity taking into account the pellet dimensions. The activation energy (E) for Li-ion diffusion was calculated. a ) was calculated from the slope of the Arrhenius plot. In a preferred embodiment, the reported ionic conductivities are measured at 25°C. In the context of the present invention, liquids are considered to be organic or aqueous compounds that are liquid at standard conditions of temperature and pressure as defined by IUPAC. The boiling points and melting points are hereby considered to be those at standard atmospheric pressure, i.e., at 101325 Pa. As will be appreciated by those skilled in the art, the presence of organic liquids can be determined via thermogravimetric analysis (TGA) or nuclear magnetic resonance (NMR) spectroscopy, and the presence of aqueous liquids can be determined via Karl Fischer titration.

[0026] As used herein, the term "solid electrolyte" refers to an electrolyte that is essentially free of any liquid. The term "essentially free of liquid" means that the solid electrolyte contains less than 10 wt. % liquid, preferably less than 7.5 wt. %, more preferably less than 5 wt. %, even more preferably less than 2.5 wt. %, and most preferably less than 1 wt. % liquid, based on the total weight of the solid electrolyte. In a more preferred embodiment, the solid electrolyte contains less than 1000 ppm liquid, preferably less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 50 ppm, and most preferably less than 10 ppm liquid, based on the total weight of the solid electrolyte.

[0027] As used herein and in the claims, the term "solid-state battery" refers to a cell or battery that contains only solid or substantially solid components, such as solid electrodes (e.g., anode and cathode) and a solid electrolyte.

[0028] solid electrolyte In a first aspect, the present invention provides a solid electrolyte having a composition according to formula (I):

[0029] Li 2+a Al a Zr 1-a X6(I)

[0030] In the formula, 0.0 <a<1であり、 X is selected from the group consisting of Cl, Br, I, and any combination of the group consisting of F, Cl, Br, and I.

[0031] In preferred embodiments, the solid electrolyte according to the invention has a range of 0.05≦a≦0.95, preferably 0.075≦a≦0.9, more preferably 0.1≦a≦0.85. In certain preferred embodiments, the solid electrolyte according to the invention has a range of 0.05≦a<0.7, preferably 0.1≦a≦0.6, more preferably 0.2≦a≦0.5.

[0032] In a preferred embodiment, the solid electrolyte is in accordance with the present invention <a<0.3、または0.3<a<1.0である。

[0033] In a preferred embodiment, the solid electrolyte according to the present invention has a range of 0.21≦a≦0.29, preferably 0.22≦a≦0.28, more preferably 0.23≦a≦0.27, even more preferably 0.24≦a≦0.26, and most preferably a is about 0.25. In a preferred embodiment, the solid electrolyte according to the present invention has a range of 0.31≦a≦0.99, preferably 0.35≦a≦0.90, and more preferably 0.39≦a≦0.80. In a particularly preferred embodiment, the solid electrolyte according to the present invention has a range of 0.35≦a≦0.70, preferably 0.37≦a≦0.60, even more preferably 0.38≦a≦0.55, and most preferably 0.40≦a≦0.50. In a highly preferred embodiment, a is about 0.40 or 0.50.

[0034] In certain preferred embodiments, a solid electrolyte according to the present invention is provided wherein X is Cl, Br, I, or a combination thereof, preferably X is Cl, Br, or a combination thereof, preferably X is Cl.

[0035] In certain preferred embodiments, the solid electrolyte is in accordance with the present invention, wherein X is Cl, Br, or I, preferably X is Cl, or Br, preferably X is Cl.

[0036] According to a preferred embodiment of the present invention, there is provided a solid electrolyte, wherein at least 50 mol% of X represents Cl, preferably at least 80 mol% of X represents Cl, and most preferably X represents Cl.

[0037] According to a preferred embodiment of the present invention, there is provided a solid electrolyte, wherein X represents Cl, Br, and I, or a combination thereof, and at least 50 mol % of X represents Cl, preferably at least 80 mol % of X represents Cl, and most preferably X represents Cl.

[0038] According to a preferred embodiment of the present invention, there is provided a solid electrolyte, wherein at least 50 mol % of X represents Br, preferably at least 80 mol % of X represents Br, and most preferably X represents Br.

[0039] According to a preferred embodiment of the present invention, there is provided a solid electrolyte, wherein X represents Cl, Br, and I, or a combination thereof, and at least 50 mol % of X represents Br, preferably at least 80 mol % of X represents Br.

[0040] According to a preferred embodiment of the present invention, there is provided a solid electrolyte, wherein at least 50 mol % of X represents I, preferably at least 80 mol % of X represents I, and most preferably X represents I.

[0041] According to a preferred embodiment of the present invention, there is provided a solid electrolyte, wherein X represents Cl, Br, and I, or a combination thereof, and at least 50 mol % of X represents I, preferably at least 80 mol % of X represents I.

[0042] In a preferred embodiment, the solid electrolyte according to the present invention has a molar ratio of Li:Al:Zr:X of (2-3):(0.01-0.99):(0.01-0.99):(5.5-6.5), preferably (2.1-2.9):(0.1-0.9):(0.1-0.9):(5.9-6.1), more preferably (2.1-2.6):(0.1-0.6):(0.4-0.9):(6).

[0043] In certain preferred embodiments, the solid electrolyte according to the present invention has a molar ratio of Li:Al:Zr:X of (2.2-2.3):(0.2-0.3):(0.7-0.8):(5.9-6.1), preferably (2.23-2.27):(0.23-0.27):(0.73-0.77):(5.9-6.1), more preferably (2.25):(0.25):(0.75):(6).

[0044] In a particularly preferred embodiment, the solid electrolyte according to the present invention has a molar ratio of Li:Al:Zr:X of (2.3-3.0):(0.3-1.0):(0.0-0.7):(5.9-6.1), preferably (2.37-2.6):(0.37-0.6):(0.4-0.63):(5.9-6.1), more preferably (2.4-2.5):(0.4-0.5):(0.5-0.6):(6).

[0045] In a preferred embodiment, the solid electrolyte according to the present invention has a purity of at least 90%, preferably at least 95%, more preferably at least 99%, as measured by XRD.

[0046] In some embodiments, the crystalline structure of the solid electrolyte may also be determined empirically, for example, by X-ray diffraction using CuKα radiation wavelengths and observing diffraction peaks around 2θ=16±1°, 29.5±1°, 26±1°, 31.5±1°, 31.5±1°, 34.0±1°, 41.0±1°, and 45.5±1°.

[0047] In a preferred embodiment, the solid electrolyte preferably has a P-31m(164) space group with lattice parameters a (Å) between 10.951 and 11.020 and c (Å) between 5.910 and 6.044, as measured by least-squares refinement and / or Rietveld analysis of the XRD profile.

[0048] In a preferred embodiment, the solid electrolyte according to the present invention has a conductivity of 0.05 to 10 mS / cm, preferably 0.1 to 2 mS / cm, more preferably 0.15 to 1 mS / cm.

[0049] In certain preferred embodiments, the solid electrolyte is in accordance with the present invention, wherein: -X is Cl; 0.05≦a≦0.7, preferably 0.1≦a≦0.6, most preferably 0.2≦a≦0.5.

[0050] In certain preferred embodiments, the solid electrolyte is in accordance with the present invention, wherein: X is Cl, 0.21≦a≦0.29, preferably 0.22≦a≦0.28, more preferably 0.24≦a≦0.26, even more preferably a=0.25.

[0051] In certain preferred embodiments, the solid electrolyte is in accordance with the present invention, wherein: X is Cl, 0.35≦a≦0.70, preferably 0.37≦a≦0.60, more preferably 0.39≦a≦0.50, even more preferably a=0.40.

[0052] In certain preferred embodiments, the solid electrolyte is in accordance with the present invention, wherein: X is Cl, 0.35≦a≦0.70, preferably 0.37≦a≦0.60, more preferably 0.45≦a≦0.55, and even more preferably a=0.50.

[0053] In certain more preferred embodiments, the solid electrolyte is according to the present invention, wherein the solid electrolyte is according to formula (II):

[0054] Li 2+a Al a Zr 1-a Cl6(II)

[0055] In certain preferred embodiments, the solid electrolyte of the present invention conforms to formula (II), where 0.05≦a≦0.7, preferably 0.1≦a≦0.6, and most preferably 0.2≦a≦0.5.

[0056] In certain preferred embodiments, the solid electrolyte of the present invention is a solid electrolyte according to formula (II), wherein: <a<0.3、または0.3<a<1.0である。

[0057] In certain preferred embodiments, the solid electrolyte of the present invention is according to formula (II), wherein 0.21≦a≦0.29, preferably 0.22≦a≦0.28, more preferably 0.24≦a≦0.26, and even more preferably a=0.25.

[0058] In certain preferred embodiments, the solid electrolyte conforms to formula (II) where 0.21≦a≦0.29, preferably 0.22≦a≦0.28, more preferably 0.23≦a≦0.27, even more preferably 0.24≦a≦0.26, and most preferably a is about 0.25. In certain preferred embodiments, the solid electrolyte conforms to formula (II) where 0.31≦a≦0.99, preferably 0.35≦a≦0.90, and more preferably 0.39≦a≦0.80.

[0059] In certain preferred embodiments, the solid electrolyte is according to formula (II), where 0.35≦a≦0.70, preferably 0.37≦a≦0.60, even more preferably 0.38≦a≦0.55, and most preferably 0.40≦a≦0.50. In highly preferred embodiments, a is about 0.40 or 0.50.

[0060] In a more preferred embodiment, the solid electrolyte according to the present invention is according to formula (II) a-g, preferably according to formula (II) a-e, more preferably according to formula (II) b-e:

[0061] [Table 1]

[0062] In certain preferred embodiments, the solid electrolyte conforms to formula (II)c, (II)e, or (II)f.

[0063] In certain preferred embodiments, the solid electrolyte of the present invention has a conductivity according to formula (II)a, preferably between 0.05 and 0.5 mS / cm, more preferably between 0.1 and 0.25 mS / cm, and most preferably about 0.11 mS / cm.

[0064] In certain preferred embodiments, the solid electrolyte of the present invention has a conductivity according to formula (II)b of preferably 0.05 to 1 mS / cm, more preferably 0.25 to 0.75 mS / cm, and most preferably about 0.52 mS / cm.

[0065] In certain preferred embodiments, the solid electrolyte of the present invention has a conductivity according to formula (II)c, preferably between 0.05 and 1 mS / cm, more preferably between 0.50 and 0.95 mS / cm, and most preferably about 0.88 mS / cm.

[0066] In certain preferred embodiments, the solid electrolyte of the present invention has a conductivity according to formula (II)d, preferably between 0.1 and 1 mS / cm, more preferably between 0.25 and 0.50 mS / cm, and most preferably about 0.41 mS / cm.

[0067] In certain preferred embodiments, the solid electrolyte of the present invention has a conductivity according to formula (II)e, preferably between 0.1 and 1 mS / cm, more preferably between 0.3 and 0.70 mS / cm, and most preferably about 0.54 mS / cm.

[0068] In certain preferred embodiments, the solid electrolyte of the present invention has a conductivity according to formula (II)f of preferably 0.1 to 1 mS / cm, more preferably 0.25 to 0.75 mS / cm, and most preferably about 0.50 mS / cm.

[0069] In certain preferred embodiments, the solid electrolyte of the present invention has a conductivity according to formula (II)g, preferably between 0.05 and 0.5 mS / cm, more preferably between 0.1 and 0.25 mS / cm, and most preferably about 0.18 mS / cm.

[0070] In certain more preferred embodiments, the solid electrolyte of the present invention is according to formula (III):

[0071] Li 2+a Al a Zr 1-a Y1 b Y 2 c (III)

[0072] In the formula, 0 <a<1であり、 Y 1 and Y 2 is independently selected from the group consisting of F, Cl, Br, and I; b+c=6, Y 1 ≠Y 2 is.

[0073] In certain more preferred embodiments, the solid electrolyte is according to formula (III), wherein 0.05≦a≦0.7, preferably 0.1≦a≦0.6, and most preferably 0.2≦a≦0.5. Even more preferably, 0.21≦a≦0.4, preferably 0.22≦a≦0.3, and even more preferably 0.23≦a≦0.26. In certain most preferred embodiments, a is about 0.25.

[0074] In certain more preferred embodiments, the solid electrolyte is according to formula (III), wherein Y 1 = F, and Y 2 is selected from the group consisting of Cl, Br, and I, preferably Cl and Br, most preferably Cl.

[0075] In certain more preferred embodiments, the solid electrolyte is according to formula (III), wherein Y 1 = Cl, and Y 2 is selected from the group consisting of F, Br, and I, preferably Br and I, more preferably Br.

[0076] In certain more preferred embodiments, the solid electrolyte is according to formula (III), wherein Y 1 =Br, and Y 2 is selected from the group consisting of F, Cl, and I, preferably Cl and I, more preferably Cl.

[0077] In certain more preferred embodiments, the solid electrolyte is according to formula (III), wherein Y 1 = I, and Y 2 is selected from the group consisting of F, Cl, and Br, preferably Cl and Br, more preferably Cl.

[0078] In certain preferred embodiments, the solid electrolyte is according to formula (III), wherein 5≦b<6, and 0 <c≦1である。

[0079] In certain highly preferred embodiments, the solid electrolyte conforms to formula (III)a-l, preferably conforms to (III)d-l, and more preferably conforms to (III)e, (III)f, (III)h, (III)i, (III)k, or (III)l:

[0080] [Table 2]

[0081] In certain preferred embodiments, the solid electrolyte conforms to formula (III)a-c.

[0082] In certain highly preferred embodiments, the solid electrolyte is according to formula (III), preferably according to formula (III)a-(III)l, more preferably according to formula (III)d-l, even more preferably according to formula (III)e, (III)f, (III)h, (III)i, (III)k, or (III)l, or according to (III)a-c, and most preferably according to formula (III)a-c, wherein b=5.0, and c=1.0, b=5.1, and c=0.9, b=5.2, and c=0.8, b=5.25, and c=0.75, b=5.3, and c=0.7, b=5.4, and c=0.6, b=5.5, and c=0.5, b=5.6, and c=0.4, b=5.7, and c=0.5, b=5.75, and c=0.25, b=5.8, and c=0.2, or b=5.9, and c=0.1, Preferably, b=5.75, and c=0.25; b=5.5, and c=0.5, or b=5.25, and c=0.75.

[0083] Manufacturing method In a second aspect, the present invention provides a method for producing a solid electrolyte, the method comprising the steps of: a) providing a set of precursors comprising Li, Al, Zr, and X; b) mixing a set of precursors to obtain a solid electrolyte; X is selected from the group consisting of Cl, Br, I, and any combination of the group consisting of F, Cl, Br, and I.

[0084] In certain preferred embodiments, the solid electrolyte is according to the second aspect of the present invention, wherein X is Cl, Br, I, or a combination thereof, preferably X is Cl, Br, or a combination thereof, more preferably X is Cl or Br, and even more preferably X is Cl.

[0085] In a preferred embodiment, the method for producing a solid electrolyte is according to the second aspect of the present invention, wherein the set of precursors is LiZ 1 , AlZ 2 3, and ZrZ 3 4, including Z 1 , Z 2 , and Z 3 is independently selected from the group consisting of Cl, Br, I, and any combination thereof.

[0086] In a preferred embodiment, the method for producing a solid electrolyte according to the second aspect of the present invention comprises the steps of: 1 , Z 2 , and Z 3is selected from the group consisting of Cl, Br, and I, preferably Cl and Br, and more preferably Z 1 =Z 2 =Z 3 =Cl, which is the same halide.

[0087] In a third aspect, the present invention provides a method for producing a solid electrolyte, preferably a solid electrolyte according to formula (III), the method comprising the following steps: a) Li, Al, Zr, Y 1 , and Y 2 providing a set of precursors comprising: b) mixing a set of precursors to obtain a solid electrolyte; In the formula, Y 1 and Y 2 is independently selected from the group consisting of F, Cl, Br, and I; Y 1 ≠Y 2 is.

[0088] In certain preferred embodiments, the solid electrolyte is according to the third aspect of the present invention, 1 and Y 2 is independently selected from the group consisting of F, Cl, Br, and I, preferably F, Cl, and Br, more preferably F and Cl; Y 1 ≠Y 2 is.

[0089] In certain preferred embodiments, the solid electrolyte is according to the third aspect of the present invention, 1 and Y 2 is independently selected from the group consisting of F, Cl, Br, and I, preferably Cl, Br, and I, more preferably Cl and Br; Y 1 ≠Y 2 is.

[0090] In a preferred embodiment, the method for producing a solid electrolyte is according to the third aspect of the present invention, wherein the set of precursors is LiZ 1 , AlZ 2 3, and ZrZ 3 4, including Z 1, Z 2 , and Z 3 is independently selected from the group consisting of F, Cl, Br, and I, preferably F, Cl, and Br, more preferably F and Cl. In certain highly preferred embodiments, Z 1 , Z 2 , and Z 3 At least two of Z are not the same halide. 1 , Z 2 , and Z 3 In certain more highly preferred embodiments, no more than two of Z 1 =Cl, Z 2 = Cl, and Z 3 =F.

[0091] In certain preferred embodiments, the method for producing a solid electrolyte according to the third aspect of the present invention comprises the steps of: 1 , Z 2 , and Z 3 is independently selected from the group consisting of F, Cl, Br, and I, preferably Cl, Br, and I, more preferably Cl and Br. In certain highly preferred embodiments, Z 1 , Z 2 , and Z 3 At least two of Z are not the same halide. 1 , Z 2 , and Z 3 At most two of them are not the same halide.

[0092] In a highly preferred embodiment, the method is according to the present invention, preferably according to the second or third aspect of the present invention, and the solid electrolyte is according to the first aspect of the present invention.

[0093] As will be understood by a person skilled in the art, all embodiments relating to the solid electrolyte according to the first aspect of the invention, relating to formula (I), formula (II), formula (III), purity levels and conductivity levels, apply equally to the method of producing the solid electrolyte according to the invention, in particular the method according to the second and / or third aspect of the invention.

[0094] In a preferred embodiment, the method according to the present invention, wherein the mixing of the set of precursors in step b) is for at least 15 minutes, preferably at least 0.5 hours, most preferably at least 1 hour.

[0095] As will be appreciated by those skilled in the art, the following embodiments apply equally to the method of the second aspect of the invention as they do to the method of the third aspect of the invention.

[0096] In a preferred embodiment, the method according to the invention, wherein the mixing of the set of precursors in step b) is for at most 60 hours, preferably at most 45 hours, most preferably at most 30 hours.

[0097] In a preferred embodiment, the method according to the present invention, wherein the mixing of the set of precursors in step b) is for 15 minutes to 60 hours, preferably 0.5 hours to 45 hours, most preferably 1 hour to 30 hours.

[0098] In a preferred embodiment, the method according to the present invention comprises mixing the set of precursors in step b) at a mixing speed of 100-1000 rpm, preferably 300-900 rpm, most preferably 400-800 rpm.

[0099] In a preferred embodiment of the method according to the present invention, the set of precursors is mixed using a mixing means. Preferably, the mixing means is a ball mill such as an electric ball mill, a vibrating ball mill, a planetary ball mill, a vibrating mixer mill or SPEX mill, a bead mill, a homogenizer, a screw mixer, a horizontal mixer, a Pulsear mixer, a jar mill, a drum mill, or a roller bench. More preferably, the mixing means is an electric ball mill, a vibrating ball mill, or a planetary ball mill, and most preferably a planetary ball mill. In a more preferred embodiment, the set of precursors is mixed by adding one or more ceramic or zirconia balls, preferably zirconia balls, more preferably yttrium-doped zirconia balls, to the set of precursors to obtain a solid electrolyte. As will be understood by those skilled in the art, the amount and size of the ceramic or zirconia balls will vary depending on the total solid content of the set of precursors.

[0100] In a preferred embodiment, the method according to the invention, wherein the mixing of the set of precursors in step b) is carried out at a temperature of at least 5° C., preferably at least 10° C., more preferably at least 15° C. A preferred embodiment is a method according to the invention, wherein the mixing of the set of precursors in step b) is carried out at a temperature below 50° C., preferably below 40° C., more preferably below 30° C. A preferred embodiment is a method according to the invention, wherein the mixing of the set of precursors in step b) is carried out at a temperature between 5 and 50° C., preferably between 10 and 40° C., more preferably between 15 and 30° C.

[0101] In a particularly preferred embodiment, a method is provided according to the invention, wherein the mixing of the set of precursors in step b) comprises: a mixing time of 15 minutes to 60 hours, preferably 0.5 hours to 45 hours, most preferably 1 hour to 30 hours, and The mixing speed is 100 to 1000 rpm, preferably 300 to 900 rpm, and most preferably 400 to 800 rpm.

[0102] Identifying items by manufacturing method In a fourth aspect, the present invention relates to a solid electrolyte according to the second aspect of the invention and / or obtainable by a method according to the third aspect of the invention.

[0103] As will be understood by those skilled in the art, all embodiments relating to the solid electrolyte according to the first aspect of the invention, and / or the method according to the second aspect of the invention, and / or the method according to the third aspect of the invention apply mutatis mutandis to the solid electrolyte obtained by the method according to the invention. For example, the various embodiments relating to formula (I), formula (II), formula (III), purity levels, and conductivity levels described herein in the context of a solid electrolyte are equally applicable to the solid electrolyte obtained by the method of making a solid electrolyte.

[0104] battery A fifth aspect of the present invention relates to a battery comprising an anode, a cathode, and a solid electrolyte layer, wherein at least one of the cathode, anode, and solid electrolyte layer comprises a solid electrolyte according to the present invention. The solid electrolyte of the present invention can be used as the solid electrolyte layer in a solid-state lithium-ion battery or solid-state lithium primary cell, or as a solid electrolyte mixed with an electrode mix for the cathode or anode.

[0105] In a preferred embodiment, the battery is a solid state battery, preferably a lithium solid state battery.

[0106] In a preferred embodiment, the solid electrolyte layer comprises a first layer consisting of a solid electrolyte according to the first aspect of the invention and / or according to the third aspect of the invention, preferably according to the first aspect of the invention.

[0107] As will be appreciated by those skilled in the art, all embodiments relating to the solid electrolyte according to the first aspect of the invention and / or the solid electrolyte obtained by the method according to the second aspect of the invention and / or the method according to the fourth aspect of the invention apply mutatis mutandis to the solid electrolyte present in the battery according to the fifth aspect of the invention. For example, the various embodiments relating to Formula (I), Formula (II), Formula (III), purity, level and conductivity level described herein in the context of the solid electrolyte are equally applicable to the solid electrolyte included in the battery according to the invention.

[0108] As will be understood by those skilled in the art, the solid electrolyte layer is a separator or membrane layer that separates the anode and cathode from each other.

[0109] A preferred embodiment is a battery according to the present invention, wherein the solid electrolyte layer comprises a second layer of a further solid electrolyte having a different composition from the solid electrolyte according to the present invention. Preferably, the further solid electrolyte having a different composition from the solid electrolyte according to the present invention is a sulfide solid electrolyte, more preferably, the further solid electrolyte having a different composition from the solid electrolyte of the present invention contains Li, P, and S. Typically, the further solid electrolyte is selected from the following sulfur-containing compounds: Li6PS5Cl (LPSCL), thio-LISICON (Li 3.25 Ge 0.25 P 0.75 S4), Li2S-P2S5-LiCl, Li2S-SiS2, LiI-Li2S-SiS2, Li2S-P2S5-LiCl, Li2S-SiS2, LiI-Li 2S-SiS2, LiI-Li2S-P2S5, LiI-Li2SP2O5, LiI-Li3PO4-P2S5, Li2S-P2S5, Li3PS4, Li7P3S 11 , LiI-Li2S-B2S3, Li3PO4-Li2S-SiS2, Li3PO4-Li2S-SiS2, Li3PO4-Li2S-SiS2, Li 10 GeP2S 12 , Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 , and / or Li7P3S 11More preferably, the further solid electrolyte, which has a different composition from the solid electrolyte according to the present invention, is an argyrodite-type solid electrolyte, most preferably Li6PS5W, with W=F, Cl, Br, I, preferably W=Cl.

[0110] A preferred embodiment is a battery according to the present invention, in which the anode comprises an active anode material (also known as an active anode material). Suitable electrochemically active anode materials are materials known in the art. For example, the anode may comprise graphitic carbon, metallic lithium, or a metal alloy containing lithium, such as a Li-In alloy, as the active anode material. Preferably, the active anode material is a Li-In alloy. A highly preferred embodiment is a battery according to the present invention, in which the anode comprises an active anode material and a solid electrolyte according to the present invention, and / or a further solid electrolyte having a different composition from the solid electrolyte of the present invention, preferably a further solid electrolyte having a different composition from the solid electrolyte.

[0111] A preferred embodiment is a battery according to the invention, wherein the cathode comprises an active cathode material (also known as an active cathode material) comprising Li, M, and O, where M comprises Ni and one or both of Mn and Co. Preferably, the active cathode material comprises Li, M, and O, where M is Ni with a content x, where 55.0 mol%≦x≦95.0 mol% relative to M, - Mn with a content y, where 0.0 mol%≦y≦40.0 mol% relative to M, Co with a content z, where 0.0 mol%≦z≦40.0 mol% relative to M, - D with a content a, where 0.0 mol%≦a≦2.0 mol% relative to M, and D is at least one element other than Li, Ni, Mn, Co, and O, wherein x+y+z+a is 100.0 mol %; More preferably, M is Ni with a content x, where 70.0 mol%≦x≦90.0 mol% relative to M, - Mn with a content y, where 10.0 mol%≦y≦30.0 mol% relative to M; Co with a content z, with respect to M, such that 10.0 mol%≦z≦30.0 mol%; - D, the content of which is a, and the content of D is 0.0 mol%≦2.0 mol% relative to M, and D is at least one element other than Li, Ni, Mn, Co, and O; wherein x+y+z+a is 100.0 mol %; Most preferably, M is Ni with a content x, where 75.0 mol%≦x≦85.0 mol% relative to M, - Mn with a content y, where 15.0 mol%≦y≦25.0 mol% relative to M, Co with a content z, with respect to M, such that 15.0 mol%≦z≦25.0 mol%; - D, the content of which is a, and the content of D is 0.0 mol%≦2.0 mol% relative to M, and D is at least one element other than Li, Ni, Mn, Co, and O; In the formula, x+y+z+a is 100.0 mol %.

[0112] In some particularly preferred embodiments, x is about 80 mol %, y is about 10 mol %, and z is about 10 mol %, also known as NMC811.

[0113] In some particularly preferred embodiments, a=0.0 mol %.

[0114] In certain preferred embodiments, the cathode active material of the present invention comprises single-crystal particles. In the context of the present invention, a particle is considered to be single-crystal if it consists of only one particle or at most five particles, preferably at most three particles, as observed by scanning electron microscopy (SEM) or transmission electron microscopy (TEM), preferably by observing the grain boundaries of the particles. A grain boundary is defined as the interface between two particles within a particle, preferably where the atomic planes of the two particles are aligned in different orientations and meet as a crystalline discontinuity.

[0115] In a particularly preferred embodiment, the present invention provides a positive electrode active material according to the present invention, the positive electrode active material being a powder comprising single particles and / or secondary particles, wherein, as observed in an SEM image, each single particle consists of only one primary particle, and each secondary particle consists of at least two primary particles and at most twenty primary particles. Preferably, at least 30% of the particles constituting the powder as observed in the SEM image, more preferably at least 50% of the particles, are single particles and / or secondary particles. The number of primary particles constituting the single particles and / or secondary particles is at least 45 μm x at least 60 μm (i.e., at least 2700 μm). 2 ), preferably at least 100 μm×100 μm (i.e., at least 10,000 μm 2 ) is determined by the field of view.

[0116] The particles in the image should be well distributed, thus avoiding overlap between particles. This can be achieved by pouring a small amount of powder sample onto an adhesive attached to the SEM sample holder and blowing air to remove excess powder.

[0117] In the context of the present invention, primary particles are distinguished from one another in SEM images by observing the grain boundaries between the primary particles, which are defined as the interface between two primary particles, where preferably the atomic planes of the two primary particles are aligned in different orientations and meet as a crystalline discontinuity.

[0118] A highly preferred embodiment is a battery according to the invention, wherein the cathode comprises a cathode active material and a solid electrolyte according to the invention and / or a solid electrolyte of the invention, preferably a further solid electrolyte having a different composition than the solid electrolyte according to the invention.

[0119] In a highly preferred embodiment, a cathode is added onto the solid electrolyte layer, and a first layer made of the solid electrolyte according to the present invention contained in the solid electrolyte layer is laminated or cast onto the cathode. In a highly preferred embodiment, an anode is added onto the solid electrolyte layer, and a second layer made of a further solid electrolyte having a different composition from the solid electrolyte according to the present invention contained in the solid electrolyte layer is laminated or cast onto the anode. In other words, a battery according to the present invention has the following configuration: the solid electrolyte layer acts as a separator between the cathode and the anode, and is, for example, "cathode / / solid electrolyte layer / / anode", preferably "cathode active material according to the present invention + solid electrolyte according to the present invention / / first layer made of the solid electrolyte according to the present invention / second layer made of a further electrolyte having a different composition from the solid electrolyte according to the present invention / / anode active material + further electrolyte having a different composition from the solid electrolyte according to the present invention", more preferably "cathode active material + solid electrolyte having a composition according to formula (I) / / first layer made of a solid electrolyte having a composition according to formula (I) / second layer made of a sulfide solid electrolyte / / anode active material + sulfide solid electrolyte". For example, but not limited to, the battery may have the following configuration: NMC811+Li 2.25 Al 0.25 Zr 0.75 Cl6 / / Li 2.25 Al 0.25 Zr 0.75Cl6 / Li6PS5Cl / / Li-In alloy+Li6PS5Cl". As will be understood by those skilled in the art, the battery of the present invention is configured such that the anode and cathode are physically separated from each other by a solid electrolyte layer, preferably the cathode is in physical contact with a first layer made of the solid electrolyte of the present invention, the anode is in physical contact with a second layer made of an additional electrolyte having a different composition than the solid electrolyte of the present invention, the cathode is not in physical contact with the second layer made of the additional electrolyte having a different composition than the solid electrolyte of the present invention, and the anode is not in physical contact with the first layer made of the solid electrolyte of the present invention.

[0120] As will be understood by those skilled in the art, the battery may further comprise one or more layers of the solid electrolyte according to the present invention, and / or a further electrolyte having a different composition from the solid electrolyte, and / or any other of the electrolytes, preferably any other electrolyte.

[0121] In one preferred embodiment, the battery according to the present invention has a capacity of at least 160 mAh / g, more preferably at least 180 mAh / g, and most preferably at least 200 mAh / g. As will be understood by those skilled in the art, capacity (Q-Q0) is measured at C / 20 from 1.9 V to 3.7 V vs. Li / In.

[0122] Battery manufacturing method A sixth aspect of the present invention relates to a method of manufacturing a battery, preferably a battery according to the fourth aspect of the present invention, comprising the steps of: (a) providing a cathode, preferably a cathode as defined herein; (b) providing an anode, preferably an anode as defined herein; (c) providing a solid electrolyte layer as defined herein; (d) Forming a battery by assembling the cathode, anode, and electrolyte into a battery.

[0123] As will be appreciated by those skilled in the art, all embodiments directed to a battery according to the sixth aspect of the present invention apply mutatis mutandis to a method of manufacturing said battery, e.g., various embodiments relating to battery configurations described herein in the context of a battery are equally applicable to a method of manufacturing said battery.

[0124] In certain highly preferred embodiments, step (d) comprises the steps of: (d1) a cathode is added onto the solid electrolyte layer, and a first layer of the solid electrolyte according to the present invention contained in the solid electrolyte is laminated or cast onto the cathode; (d2) An anode is added onto the solid electrolyte layer, and a second layer of a further solid electrolyte having a different composition from the solid electrolyte of the present invention contained in the solid electrolyte layer is laminated or cast onto the anode.

[0125] In certain highly preferred embodiments, step (d) comprises the steps of: (d1') an anode is added onto the solid electrolyte layer, and a second layer of a further solid electrolyte having a composition different from the solid electrolyte of the present invention contained in the solid electrolyte layer is laminated or cast onto the anode; (d2') A cathode is added onto the solid electrolyte layer, and a first layer of the solid electrolyte according to the present invention contained in the solid electrolyte layer is laminated or cast onto the cathode.

[0126] use A seventh aspect of the present invention relates to the use of a solid electrolyte according to the present invention in a battery, preferably a solid-state battery, most preferably a lithium solid-state battery.

[0127] An eighth aspect of the invention relates to the use of a battery according to the invention in any one of a portable computer, a tablet, a mobile phone, an energy storage system, an electric vehicle, or a hybrid electric vehicle, preferably in a vehicle or a hybrid electric vehicle.

[0128] The present invention is further illustrated in the following examples.

[0129] [Example 1] Test method description Synthesis protocol All synthetic work and sample processing were carried out in an Ar-filled glovebox. For each exemplary stoichiometric ratio of reagents, LiCl (ultra-dry, 99.9% metal basis, Alfa Aesar), ZrCl4 (ultra-dry, 99.5% metal basis, Alfa Aesar), and AlCl3 (ultra-dry, 99.99% metal basis, Alfa Aesar) were mixed to obtain 1 g batches of precursor in a 45 mL ball mill jar. A stochastic ratio of LiCl, ZrCl4, and AlF3 was used for EX8. The precursor was transferred to a Fritsch Pulverisette 7 Classical Line 45 mL zirconia ball milling jar along with ten 10 mm diameter yttrium-doped zirconia balls (ball:powder ratio was 1:40 or 1:30 by mass). The precursor was milled at 600 rpm for a total effective time of 10 h to obtain the solid electrolyte.

[0130] X-ray diffraction All samples were prepared using Cu-K α Measurements were performed at room temperature using a Bruker D8 diffractometer with radiation (λCu = 1.5418 Å). Because all samples are moisture sensitive, preparations were performed in an Ar-filled glove box and placed in an airtight sample holder with a Be window (250 μm thick).

[0131] Impedance spectroscopy Electrochemical impedance spectroscopy measurements were performed using a frequency response analyzer (MTZ-35, Biologic) and an intermediate temperature system (ITS, Biologic). The powder was pelletized between two carbon papers using a 6 mm diameter die in a uniaxial hydraulic press (approximately 1.5 tons). The pellets were loaded into an airtight sample holder (CESH, Biologic) in an Ar-filled glove box and measured at temperatures ranging from 25 to 75 °C. A frequency range of 35 MHz to 1 Hz and an applied voltage of 50 mV were used. Ionic conductivity was determined by extracting the resistance from the Nyquist plot and calculating the conductivity taking into account the pellet dimensions. The activation energy (E) for Li-ion diffusion was calculated. a ) was calculated from the slope of the Arrhenius plot. The reported conductivity values ​​are measured at 25°C.

[0132] Battery assembly All examples were carried out in an Ar-filled glove box. Bare single crystal NMC811 was used as the cathode active material. The cathode composite consisted of 70 wt. % NMC811 and 30 wt. % solid electrolyte (LiZrCl (=LZC), or Li 2.25 Al 0.25 Zr 0.75 The positive electrode composite was prepared by hand grinding lithium-indium alloy (either LiCl6 (=LAZC)) in a mortar without any carbon additives. The positive electrode composite was prepared by hand grinding lithium-indium alloy (Li ... 0.5 The solid electrolyte was hand-ground in a mortar in a weight ratio of 60 wt% In and 40 wt% Li6PS5Cl (NEI Corporation). The cell was assembled between two stainless steel pistons (10 mm diameter). The first 50 mg of solid electrolyte was pressed at 1 ton for 1 minute to form a separate layer. Depending on the cell configuration, this step was repeated twice to form two layers of separator (single-layer configuration, one step with Li6PS5Cl (NEI Corporation) or two-layer configuration, one step with a halide-based solid electrolyte (Li2ZrCl6 (=LZC) or Li 2.25 Al 0.25 Zr 0.75The cathode composite was then split into two parts, one side corresponding to 12 mg of cathode active material (LiZrCl(=LZC), or Li 2.25 Al 0.25 Zr 0.75 60 mg of anode composite was added to the other side (in the bilayer system on the Li6PS5Cl side) and 60 mg of anode composite was added to the other side (in the bilayer system on the Li6PS5Cl side). Finally, a pressure of 3 tons was applied for 3 minutes. The entire stack was then placed in an airtight jar with a vice to maintain an internal pressure of 1 ton. The cells were cycled at C / 20 from 1.9 V to 3.7 V vs. Li / In. Overall, the following cells were prepared: Cell 1: NMC+LAZC / LAZC / Arg / Li-In+Arg (LAZC bilayer) Cell 2: NMC+LAZC / / Arg / / Li-In+Arg (LAZC monolayer) Cell 3: NMC+LZC / / LZC / Arg / / Li-In+Arg (LZC double layer) Cell 4: NMC+LZC / / Arg / / Li-In+Arg (LZC monolayer)

[0133] Example Table 1 shows the overall formulas of examples synthesized via the general synthesis protocol described above, along with their corresponding ionic conductivities.

[0134] Table 1: Overall formula and ionic conductivities of CEX1 and EX1-7

[0135] [Table 3]

[0136] The profile agreement of the powder X-ray diffraction data suggests that the crystal structure is conserved for EX1, 3, 4, and 6. No peaks corresponding to precursor or other impurity phases are observed (see Figure 1). The ionic conductivity of CEX2 is 10 at 120 °C. -9For CEX3, Li 2.25 Al 0.25 Zr 0.75 F6 is not synthesized as expected, but rather a mixture of crystal structures (trigonal-Li 2+x Al x Zr 1-x F6(P-31m), and monoclinic-Li 2+y Al y Zr 1-y F6 (P121 / c1)) is obtained in a weight ratio of approximately 1:1. The ionic conductivity of this mixture is 10 -8 S.cm -1 , 10 at 120°C -5 S.cm -1 is.

[0137] Table 2 shows the capacities of cells 1-4 after one cycle at C / 20 between 1.9V and 3.7V vs. Li / In1. Figure 2 is a graphical representation of Table 2.

[0138] Table 2: Capacity of cells 1-4 after one cycle at C / 20 from 1.9V to 3.7V vs. Li / In

[0139] [Table 4]

Claims

1. A solid electrolyte having a composition according to formula (I), Li ２＋ａ Al ａ Z １－ａ X ６ (I) wherein 0.2<a<0.3, or 0.3<a<1.0; A solid electrolyte wherein X is selected from the group consisting of Cl, Br, I, and any combination of the group consisting of F, Cl, Br, and I.

2. 10. The solid electrolyte of claim 1, wherein X is Cl, Br, I, or a combination thereof.

3. 3. The solid electrolyte according to claim 1, wherein 0.21≦a≦0.29, preferably 0.22≦a≦0.28, more preferably 0.24≦a≦0.26, even more preferably a=0.

25.

4. 3. The solid electrolyte according to claim 1, wherein 0.31≦a≦0.99, preferably 0.35≦a≦0.90, more preferably 0.39≦a≦0.

80.

5. 5. The solid electrolyte according to claim 4, wherein 0.35≦a≦0.70, preferably 0.37≦a≦0.60, more preferably 0.40≦a≦0.

50.

6. 6. The solid electrolyte according to claim 1, wherein X is selected from the group consisting of Cl, Br, and I, preferably Cl and Br, and more preferably X is Cl.

7. 7. The solid electrolyte of claim 1, having a composition according to formula (II): Li ２＋ａ Al ａ h １－ａ 3l ６ (99)

8. 10. The solid electrolyte of any one of the preceding claims having a composition according to formula (II)c, (II)e, or (II)f. Table 1

9. A solid electrolyte having a composition according to formula (III): Li ２＋ａ Al ａ Z １－ａ Y １ ｂ Y ２ ｃ (I1I) wherein 0<a<1; Y １ and Y ２ is independently selected from the group consisting of F, Cl, Br, and I; b+c=6, Y １ ≠Y ２ and Y １ = F and Y ２ is independently selected from the group consisting of Cl, Br, and I.

10. A method for producing a solid electrolyte according to any one of claims 1 to 9, comprising the steps of: a) providing a set of precursors comprising Li, Al, Zr, and X; b) mixing the set of precursors to obtain the solid electrolyte, wherein X is selected from the group consisting of Cl, Br, I, and any combination of the group consisting of F, Cl, Br, and I, preferably X is Cl, Br, I, or a combination thereof, more preferably X is Cl, Br, or a combination thereof, and even more preferably X is Cl.

11. The set of precursors is LiZ １ , AlZ ２ ３ , and ZrZ ３ ４ including Z １ , Z ２ , and Z ３ are independently selected from the group consisting of F, Cl, Br, I, and any combination thereof; Z, Z ２ , and Z ３ The method of claim 10 , wherein:

12. A battery comprising an anode, a cathode, and a solid electrolyte layer, wherein at least one of the cathode, the anode, and the solid electrolyte layer comprises the solid electrolyte according to any one of claims 1 to 9.

13. The battery according to claim 12, wherein the solid electrolyte layer comprises a first layer made of the solid electrolyte according to any one of claims 1 to 9.

14. 14. The battery of claim 13, wherein the solid electrolyte layer comprises a second layer of a further solid electrolyte having a different composition from the solid electrolyte of any one of claims 1 to 9.

15. The further solid electrolyte having a composition different from that of the solid electrolyte according to any one of claims 1 to 9 is a sulfide solid electrolyte, preferably an argyrodite-type solid electrolyte, more preferably Li ６ P.S. ５ 15. The battery of claim 14, wherein the Cr is Cl.

16. A method for manufacturing a battery, preferably a battery according to any of claims 11 to 15, comprising the following steps: (a) providing a cathode; (b) providing an anode; (c) providing a solid electrolyte layer as defined in claims 12 to 15; (d) forming the battery by assembling the cathode, the anode, and the solid electrolyte layer into a battery.

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