CN117497833A - Solid ion conductor compound, electrochemical cell and method for preparing solid ion conductor compound - Google Patents

Solid ion conductor compound, electrochemical cell and method for preparing solid ion conductor compound Download PDF

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CN117497833A
CN117497833A CN202310879959.6A CN202310879959A CN117497833A CN 117497833 A CN117497833 A CN 117497833A CN 202310879959 A CN202310879959 A CN 202310879959A CN 117497833 A CN117497833 A CN 117497833A
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ion conductor
metal
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solid ion
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崔源成
李锡守
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • 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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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/455—Phosphates containing halogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

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Abstract

The present invention relates to solid ion conductor compounds, electrochemical cells and methods of making solid ion conductor compounds. The solid ion conductor compound includes a compound represented by formula 1, wherein in formula 1M is at least one alkali metal, M' is at least one of a divalent metal, a trivalent metal, a tetravalent metal, a pentavalent metal, a hexavalent metal, or a combination thereof, X is at least one halogen, T is at least one of a monovalent anion or a divalent anion, Z is at least one of a trivalent anion, 2.ltoreq.k.ltoreq.6, 1.ltoreq.l.ltoreq.2, -3.ltoreq.m.ltoreq.3, 0<n≤1，0≤o<3，0<p<2, -3.ltoreq.q.ltoreq.3, and 0<(3+m+kn-lo-3p+q). 1M 3+m+(l‑1)o+2p (M' k+ ) n X 3+m+kn‑lo‑3p+q T l‑ o Z 3‑ p 。

Description

Solid ion conductor compound, electrochemical cell and method for preparing solid ion conductor compound
Technical Field
The disclosure relates to solid ion conductor compounds, solid electrolytes comprising the solid ion conductor compounds, lithium batteries comprising the solid ion conductor compounds, and methods of preparing the solid ion conductor compounds.
Background
An all-solid lithium battery includes a solid electrolyte. Since the all-solid lithium battery may not contain a flammable organic solvent, the all-solid lithium battery has excellent stability.
Solid electrolyte materials in the related art may not be sufficiently stable for lithium metal. In addition, the lithium ion conductivity of the solid electrolyte in the related art is lower than that of the liquid substitute. Thus, there remains a need for improved solid electrolytes.
Disclosure of Invention
A solid ion conductor compound is provided which has excellent lithium ion conductivity by having a novel composition.
Additional aspects will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to one aspect of the disclosure, the solid ion conductor compound includes a compound represented by formula 1:
1 (1)
M 3+m+(l-1)o+2p (M' k+ ) n X 3+m+kn-lo-3p+q T l- o Z 3- p
Wherein, in the formula 1,
m is at least one alkali metal, and the alkali metal,
m' is at least one of a divalent metal, a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal,
x is at least one halogen, and the halogen is at least one halogen,
t is at least one of a monovalent anion or a divalent anion,
z is at least one of trivalent anions,
k is more than or equal to 2 and less than or equal to 6, l is more than or equal to 1 and less than or equal to 2, m is more than or equal to 3 and less than or equal to 3, n is more than or equal to 0 and less than or equal to 1, o is more than or equal to 0 and less than or equal to 3, p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 3 and less than or equal to 0 (3+m+kn-lo-3p+q).
According to an embodiment, in formula 1, M comprises at least one of Li, na, K, rb, or Cs. For example, M is at least one of Li or Na.
According to an embodiment, in formula 1, M' includes at least one of Mg, zn, ca, sr, ba, eu, Y, gd, in, er, la, yb, ce, ho, sn, th, nb, mo, W, sb, bi, zr, hf, ti, or Si.
According to an embodiment, in formula 1, X comprises at least one of F, cl, br, or I.
According to an embodiment, in formula 1, Z comprises PO 4 3- 、(C 6 H 5 O 7 ) 3- 、PS 4 3- 、[Fe(CN)] 3- 、[Ag(S 2 O 3 ) 2 ] 3- 、N 3- Or P 3- At least one of (a) and (b). For example, Z comprises a trivalent polyatomic ion.
According to an embodiment, in formula 1, T comprises NO 3 - 、CH 3 COO - 、OH - 、HCO 3 - 、CrO 4 2- 、SO 4 2- 、CO 3 2- Or BH 4 - At least one of (a) and (b).
According to an embodiment, in formula 1, 3.ltoreq.k.ltoreq.5.
According to an embodiment, in formula 1, -3.ltoreq.m.ltoreq.0.5.
According to an embodiment, 0<p is less than or equal to 0.3 in formula 1.
According to an embodiment, in formula 1, 2< (3+m + (l-1) o+2p) <3.
According to an embodiment, in formula 1, 5.8.ltoreq.3+m+kn-lo-3p+q <6.
According to an embodiment, formula 1 is represented by formula 2:
2, 2
(Li 1-h M h ) 3+m+(l-1)o+2p (M' k+ ) n X 3+m+kn-lo-3p+q T l- o ((PO 4 ) 1-i Z' i ) p
Wherein, in the formula 2,
m is at least one alkali metal different from Li,
z' is different from PO 4 3- At least one of the trivalent anions of (c) is used,
m' is at least one of a divalent metal, a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal,
x is at least one halogen, and the halogen is at least one halogen,
t is at least one of a monovalent anion or a divalent anion, and
K is more than or equal to 2 and less than or equal to 6, l is more than or equal to 1 and less than or equal to 2, m is more than or equal to 3, n is more than or equal to 0 and less than or equal to 1, o is more than or equal to 0 and less than or equal to 3, p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 3,0< (3+m+kn-lo-3p+q), h is more than or equal to 0 and less than or equal to 1.
According to an embodiment, in formula 2, M is Na.
According to an embodiment, in formula 2, 0.ltoreq.h.ltoreq.0.5.
According to an embodiment, in formula 2, 0.ltoreq.i.ltoreq.0.5.
According to an embodiment, formula 1 is represented by formula 3:
3
(Li 1-h M h ) 3+m+(l-1)o+2p ((Zr) 1-j M' j k+ ) n X 3+m+kn-lo-3p+q T l- o ((PO 4 ) 1-i Z' i ) p
Wherein, in the formula 3,
m is at least one alkali metal different from Li,
z' is different from PO 4 3- At least one of the trivalent anions of (c) is used,
m' is at least one of a divalent metal, a trivalent metal, a tetravalent metal, a pentavalent metal, and a hexavalent metal different from Zr,
x is at least one halogen, and the halogen is at least one halogen,
t is at least one of a monovalent anion or a divalent anion, and
k is more than or equal to 2 and less than or equal to 6, l is more than or equal to 1 and less than or equal to 2, m is more than or equal to 3, n is more than or equal to 0 and less than or equal to 1, o is more than or equal to 0 and less than or equal to 3, p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 3,0< (3+m+kn-lo-3p+q), h is more than or equal to 0 and less than or equal to 1, i is more than or equal to 0 and less than or equal to j is more than or equal to 1.
According to an embodiment, in formula 3, 0.ltoreq.j.ltoreq.0.5.
According to an embodiment, the solid ion conductor compound has diffraction peaks at diffraction angles of 16 ° 2θ±0.5° 2θ, 20 ° 2θ±0.5° 2θ, 30 ° 2θ±0.5° 2θ, 32 ° 2θ±0.5° 2θ, 42 ° 2θ±0.5° 2θ, and 50 ° 2θ±0.5° 2θ when analyzed by X-ray diffraction using cukα radiation.
According to an embodiment, the solid ion conductor compound has an ionic conductivity of about 0.3 millisiemens/cm or greater at a temperature of about 25 ℃.
According to an embodiment, the solid ion conductor compound comprises at least one of a crystalline phase and an amorphous phase.
According to an embodiment, the solid ion conductor compound comprises crystals belonging to the P3-m1 space group.
According to an embodiment, the solid ion conductor compound has a and c lattice constants that are larger than the a and c lattice constants of a solid ion conductor compound that does not include a trivalent anion represented by Z.
According to an embodiment, the solid ion conductor compound is Li 2.1 ZrCl 5.95 (PO 4 ) 0.05 、Li 2.02 ZrCl 5.99 (PO 4 ) 0.01 、Li 2.04 ZrCl 5.98 (PO 4 ) 0.02 、Li 2.08 ZrCl 5.96 (PO 4 ) 0.04 、Li 2.12 ZrCl 5.94 (PO 4 ) 0.06 、Li 2.2 ZrCl 5.9 (PO 4 ) 0.1 、Li 2.15 Zr 0.8 Y 0.2 Cl 5.95 (PO 4 ) 0.05 、Li 2.45 Zr 0.5 Y 0.5 Cl 5.95 (PO 4 ) 0.05 、Li 2.22 ZrCl 5.89 (PO 4 ) 0.11 、Li 2.24 ZrCl 5.88 (PO 4 ) 0.12 、Li 2.3 ZrCl 5.85 (PO 4 ) 0.15 、Li 2.4 ZrCl 5.8 (PO 4 ) 0.2 、Li 2.6 ZrCl 5.7 (PO 4 ) 0.3 Or Li (lithium) 2.1 ZrCl 5.95 (PS 4 ) 0.05 。
According to another aspect of the disclosure, a method of preparing a solid ion conductor compound comprises: providing a mixture comprising: a halide compound containing an M element, a halide compound containing an M 'element, and a compound containing a Z anion, wherein the M element is at least one alkali metal, the M' element is at least one of a divalent metal, a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal, and the Z anion is at least one of a trivalent anion; and
the mixture is treated in a solid phase to produce the solid ion conductor compound.
According to an embodiment, treating the mixture in a solid phase to produce the solid ion conductor compound comprises ball milling the mixture under a dry and inert atmosphere.
According to an embodiment, the ball milling is performed for a first period of time, and the ball milling further comprises a rest (rest) period of time after the first period of time, wherein the first period of time and the rest period of time are repeated.
According to another aspect of the disclosure, an electrochemical cell includes: a positive electrode layer including a positive electrode active material;
a negative electrode layer including a negative electrode active material; and
a solid electrolyte layer between the positive electrode layer and the negative electrode layer and comprising a solid electrolyte, wherein at least one of the positive electrode layer or the solid electrolyte layer comprises the solid ion conductor compound.
According to an embodiment, the solid electrolyte layer comprises a sulfide solid electrolyte.
According to an embodiment, the positive electrode active material layer includes at least one of positive electrode active materials represented by: liNi x Co y Al z O 2 Wherein 0 is<x<1，0<y<1，0<z<1, and x+y+z=1; or LiNi x' Co y' Mn z' O 2 Wherein 0 is<x'<1，0<y'<1，0<z'<1, and x ' +y ' +z ' =1.
According to an embodiment, the negative electrode active material layer includes lithium metal.
According to an embodiment, when charged and discharged at 0.1C in the range of about 2.5 volts to about 4.2 volts, the discharge capacity is maintained at about 93% or more for 20 cycles as compared to the initial discharge capacity.
According to an embodiment, the electrochemical cell is an all-solid secondary battery.
Drawings
The above and other aspects, features and advantages of the disclosure will become more apparent from the following description considered in conjunction with the accompanying drawings in which:
fig. 1 is a plot of intensity (arbitrary unit, a.u.) versus diffraction angle (° 2θ) and shows the results of X-ray diffraction (XRD) analysis using Cu Ka radiation of the solid ion conductor powders of examples 1, 2, 4, 5, and 6 and comparative example 1;
FIG. 2 is a plot of intensity (arbitrary units) versus diffraction angle (° 2θ) and shows an enlarged plot of the XRD spectrum of FIG. 1 of peaks at diffraction angles of 32.3 ° 2θ;
figure 3 is a graph of lattice constants (angstroms,) For Li 2+2x Zr 1-x Cl 6-x (PO 4 ) x The graph of x in (a) shows the results of calculation of lattice constants of the crystal structures of the solid ion conductor powders of examples 1, 2, 4, 5, and 6 and comparative example 1;
FIG. 4 shows ion conductivity (Siemens/cm, S.cm) -1 ) For Li 2+2x Zr 1-x Cl 6-x (PO 4 ) x The graph of x in (a) shows the ionic conductivity as a function of the molar ratio of trivalent anions for the solid ion conductor powders of examples 1-6 and 10-14 and comparative example 1;
FIG. 5 shows specific capacity (mAh.g/g -1 ) A graph of the number of cycles, and shows the results of charging and discharging of the all-solid batteries of example 15 and comparative example 8;
FIG. 6 shows specific capacity (mAh.g -1 ) A graph of the C-rate ratio showing the rate characteristics of all solid batteries of example 15 and comparative examples 8 and 9;
fig. 7 is a schematic view of an embodiment of an all-solid secondary battery;
fig. 8 is a schematic view of an embodiment of an all-solid secondary battery; and
FIG. 9 is a graph of intensity (arbitrary units) versus binding energy (electron volts, eV), as demonstrated by X-ray photoelectron spectroscopy (XPS) analysis of example 1 4 The presence of ions.
Detailed Description
Reference will now be made in detail to the embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as limited to the descriptions set forth herein. Accordingly, the embodiments are described below to illustrate various aspects by referring only to the drawings. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, "a," "an," "the," and "at least one" are not intended to be limiting of amounts, and are intended to include both singular and plural unless the context clearly indicates otherwise. For example, an "element" has the same meaning as "at least one element" unless the context clearly dictates otherwise. The "at least one (species)" will not be construed as limiting the "one (species)". "or" means "and/or". As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. The expression "at least one of the elements" when preceding or following a list of elements, for example, modifies the entire list of elements and does not modify individual elements of the list.
Various embodiments are shown in the drawings. The inventive concept may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the inventive concept to those skilled in the art. Like reference numerals refer to like parts.
It will be understood that when an element is referred to as being "on" another element, it can be directly on the other element or intervening elements may be present. In contrast, when an element is referred to as being "directly on" another element, there are no additional elements interposed therebetween.
The terms "first," "second," "third," and the like may be used herein to describe various elements, components (parts), regions, layers, sections, and/or areas, but these elements, components (parts), regions, layers, sections, and/or areas should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or area from another element, component, region, layer or area. Thus, a first element, component, region, layer, section or area discussed below could be termed a second element, component, region, layer, section or area without departing from the teachings described herein.
It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the inventive concepts. The term "and/or" as used herein may include any and all combinations of one or more of the enumerated items. As used in this detailed description, the term "comprising" indicates the presence of a specified feature, region, integer, step, action, element, and/or component (means), and does not preclude the presence or addition of one or more additional features, regions, integers, steps, actions, elements, components (means), and/or groups thereof.
Spatially relative terms, such as "below … …," "lower," "bottom," "above … …," "higher," "top," and the like, are used herein to readily describe one element or feature's relationship to another element or feature. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, when the device in the figures is turned over, elements described as "under" or "beneath" additional elements or features would then be oriented "over" the additional elements or features. Thus, the exemplary term "under … …" may encompass both upward and downward directions. The devices may be arranged in different directions (rotated 90 degrees or in different directions), and spatially relative terms used herein may be construed accordingly.
As used herein, "about" or "approximately" includes the stated values and is meant to be within an acceptable range of deviation from the particular values as determined by one of ordinary skill in the art in view of the measurements in question and the errors associated with the measurement of the particular quantities (i.e., limitations of the measurement system). For example, "about" may mean within one or more standard deviations, or within ±30%, 20%, 10%, or 5%, relative to the stated values. The endpoints of the range may each be independently selected.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In addition, it will be understood that terms, as defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense.
Embodiments are described herein with reference to schematic cross-sectional views of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, the embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated in the specification but are to include deviations in shapes that result, for example, from manufacturing. For example, an area depicted or described as flat may typically have rough and/or nonlinear features. Moreover, the sharp illustrated corners may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the claims.
"group" means a group of the periodic Table of elements according to the International Union of Pure and Applied Chemistry (IUPAC) group 1-18 taxonomy.
Although particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not presently contemplated may be appreciated by the applicant or by those of ordinary skill in the art. Accordingly, the appended claims as filed and as modified are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.
Hereinafter, a solid ion conductor compound, a solid electrolyte including the solid ion conductor compound, an electrochemical cell including the solid electrolyte, and a method of preparing the solid ion conductor compound according to at least one embodiment will be described in further detail.
Solid ion conductor compound
The solid ion conductor compound includes a compound represented by formula 1:
1 (1)
M 3+m+(l-1)o+2p (M' k+ ) n X 3+m+kn-lo-3p+q T l- o Z 3- p
Wherein in formula 1, M is at least one alkali metal.
According to an embodiment, M may include at least one of Li, na, K, rb, or Cs. For example, M may include at least one of Li or Na. According to an embodiment, M may include Li and Na. In embodiments, the molar ratio of Na/(li+na) may be less than about 0.5. That is, when M further includes an additional element other than Li, the molar ratio of the additional element may be smaller than that of Li. According to an embodiment, when some of Li is replaced with Na, li ion channels may expand according to expansion of crystal lattice, and as a result, lithium ion conductivity may be improved.
In formula 1, M' is at least one of a divalent metal, a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal. According to an embodiment, M' may comprise Mg, zn, ca, sr, ba, eu, Y, gd, in, er, la, yb, ce, ho, sn, th, nb, mo, W, sb, bi, zr, hf, ti, or Si. For example, M' may include Mg, ca, er, sr, ba, Y, gd, er, la, ho, zr, hf, ti, ce, or Si, but the embodiment is not limited thereto.
In formula 1, X may be at least one halogen. According to an embodiment, X may be at least one of F, cl, br, or I. For example, X may be at least one of Br or Cl, but the embodiment is not limited thereto. According to another embodiment, X may be Cl, and some of the Cl may optionally be replaced with Br. In embodiments, the molar ratio of Br/(cl+br) may be about 0.5 or less. When the molar ratio of Br is smaller than that of Cl, excessive amorphization in the product can be suppressed, and thus, deterioration of ion conductivity can be prevented.
In formula 1, T may be at least one of a monovalent anion or a divalent anion. For example, T may be NO 3 - 、CH 3 COO - 、OH - 、HCO 3 - 、CrO 4 2- 、SO 4 2- 、CO 3 2- Or BH 4 - But the embodiment is not limited thereto.
In formula 1, Z is at least one of trivalent anions. According to embodiments, Z may comprise a trivalent monoatomic anion, or a trivalent polyatomic anion. For example, Z may be a trivalent polyatomic anion. According to an embodiment, Z may comprise PO 4 3- 、(C 6 H 5 O 7 ) 3- 、PS 4 3- 、[Fe(CN)] 3- 、[Ag(S 2 O 3 ) 2 ] 3- 、N 3- Or P 3- . For example, Z may comprise PO 4 3- 、(C 6 H 5 O 7 ) 3- 、PS 4 3- 、[Fe(CN)] 3- Or [ Ag (S) 2 O 3 ) 2 ] 3- But the embodiment is not limited thereto.
In formula 1, k, l, m, n, o and p are each independently 2.ltoreq.k.ltoreq.6, 1.ltoreq.l.ltoreq.2, -3.ltoreq.m.ltoreq.3, 0< n.ltoreq.1, 0.ltoreq.o <3,0< p.ltoreq.2, -3.ltoreq.q.ltoreq.3, and 0< (3+m+kn-lo-3p+q). In one aspect, k is the cation valence of the M element, and for example, 2.5.ltoreq.k.ltoreq.5.5, or 3.ltoreq.k.ltoreq.5. In one aspect, l is the anionic valence of the T element, and for example, T may be 1 or 2. In one aspect, M is a variable determined according to the initial amount of halide compound of the starting material containing M element during synthesis, and for example, -2.ltoreq.m.ltoreq.2 or-3.ltoreq.m.ltoreq.0.5. In one aspect, n may be the molar ratio of M' elements, and for example, 0.5.ltoreq.n.ltoreq.1. In one aspect, o may be the molar ratio of the T element, and o may be, for example, 0. In one aspect, p may be the molar ratio of Z anions, and for example, 0<p.ltoreq.0.3, 0< p.ltoreq.0.2, 0< p.ltoreq.0.1, 0.01.ltoreq.p.ltoreq.0.3, 0.01.ltoreq.p.ltoreq.0.2, or 0.01.ltoreq.p.ltoreq.0.1. In one aspect, q is a variable determined according to the initial input of the halide compound of the starting material containing the M' element during synthesis, and for example, -3.ltoreq.q.ltoreq.2, -2.ltoreq.q.ltoreq.1, or-3.ltoreq.q.ltoreq.0.5. In one aspect, 3+m+kn-lo-3p+q may be a molar ratio of halogen, and for example, 5.8.ltoreq.3+m+kn-lo-3p+q) <6 or 5.9.ltoreq.3+m+kn-lo-3p+q) <6. According to an embodiment, in formula 1, 3+m + (l-1) o+2p can be a molar ratio of M, and 2< (3+m + (l-1) o+2p) <3. For example, 2< (3+m + (l-1) o+2p) <2.5.
When the solid ion conductor compound including the compound represented by formula 1 satisfies the above composition, the solid ion conductor compound may have improved lifetime characteristics and ion conductivity.
According to an embodiment, formula 1 may be represented by formula 2:
2, 2
(Li 1-h M h ) 3+m+(l-1)o+2p (M' k+ ) n X 3+m+kn-lo-3p+q T l- o ((PO 4 ) 1-i Z' i ) p
Wherein in formula 2, M ', X, M, n, o, p, k, l, q and T can be understood by reference to the descriptions of M', X, M, n, o, p, k, l, q and T, respectively, provided herein,
m may be at least one alkali metal other than Li,
z' may be other than PO 4 3- At least one of the trivalent anions, and
h <1 > is 0.ltoreq.h <1, and i <1 is 0.ltoreq.i <1.
According to an embodiment, M may be Na. According to an embodiment, h may satisfy 0.ltoreq.h.ltoreq.0.5 or 0.5.ltoreq.h <1. According to an embodiment, i may satisfy 0.ltoreq.i.ltoreq.0.5 or 0.5.ltoreq.i <1.
According to an embodiment, formula 1 may be represented by formula 3:
3
(Li 1-h M h ) 3+m+(l-1)o+2p ((Zr) 1-j M' j k+ ) n X 3+m+kn-lo-3p+q T l- o ((PO 4 ) 1-i Z' i ) p
Wherein, in formula 3, X, m, n, o, p, k, l, q, and T can be understood by reference to the descriptions of X, m, n, o, p, k, l, q, and T, respectively, provided herein,
m may be at least one alkali metal different from Li,
z' may be other than PO 4 3- At least one of the trivalent anions of (c) is used,
m' may be at least one of a divalent metal, trivalent metal, tetravalent metal, pentavalent metal, and hexavalent metal other than Zr, and
0≤j<1。
According to an embodiment, j may satisfy 0.ltoreq.j.ltoreq.0.5 or 0.5.ltoreq.j <1.
When analyzed by X-ray diffraction (XRD) using cukα radiation, the solid ion conductor compound may have diffraction peaks at diffraction angles of 16 ° 2θ±0.5° 2θ, 20 ° 2θ±0.5° 2θ, 30 ° 2θ±0.5° 2θ,32 ° 2θ±0.5° 2θ, 42 ° 2θ±0.5° 2θ, and 50 ° 2θ±0.50° 2θ.
According to an embodiment, when the solid ion conductor compound has an increased amount of Z anions, the peak of the diffraction angle of 32 ° 2θ±0.5° 2θ may be shifted toward a lower diffraction angle.
According to embodiments, the solid ion conductor compound may have increased a and c-axis lattice constants as compared to a compound that does not include a trivalent anion represented by Z.
For example, the solid ion conductor compound may have an increase in the a-axis of up to aboutAnd up to about +.added in the c-axis>Is a lattice constant of (c).
According to embodiments, the solid ion conductor compound may have at least one of a crystalline phase or an amorphous phase, and may include an amorphous phase.
For example, the solid ion conductor compound may include a layered rock salt crystal structure as a crystalline phase. For example, the layered rock salt crystal structure may include a deformed (distorted) layered rock salt crystal structure.
According to embodiments, the solid ion conductor compound may include a crystalline structure belonging to the P3-m1 space group as a crystalline phase.
According to embodiments, the solid ion conductor compound may have a chemical composition of about 3.0X10 at room temperature, e.g., at a temperature of about 25℃ -4 Siemens/centimeter (S/cm) or greater. For example, the solid ion conductor compound may have a temperature of about 25 ℃ of about 3.2 x 10 -4 S/cm or greater, about 4.0X10 -4 S/cm or greater, about 5.0X10 -4 S/cm or greater, about 6.0X10 -4 S/cm or greater, about 7.0X10 -4 S/cm or greater, about 8.0X10 -4 S/cm or greater, about 9.0X10 -4 S/cm or greater, or about 1.0X10 -3 S/cm or greater. In one aspect, the solid ion conductor compound can have a temperature of about 3.0X10 at about 25 DEG C -4 S/cm to about 5.0X10 -1 S/cm, about 5.0X10 -4 S/cm to about 3.0X10 -1 S/cm, about 7.0X10 -4 S/cm to about 1.0X10 -1 S/cm ionic conductivity.
According to an embodiment, the solid ion conductor compound may be Li 2.1 ZrCl 5.95 (PO 4 ) 0.05 、Li 2.02 ZrCl 5.99 (PO 4 ) 0.01 、Li 2.04 ZrCl 5.98 (PO 4 ) 0.02 、Li 2.08 ZrCl 5.96 (PO 4 ) 0.04 、Li 2.12 ZrCl 5.94 (PO 4 ) 0.06 、Li 2.2 ZrCl 5.9 (PO 4 ) 0.1 、Li 2.15 Zr 0.8 Y 0.2 Cl 5.95 (PO 4 ) 0.05 、Li 2.45 Zr 0.5 Y 0.5 Cl 5.95 (PO 4 ) 0.05 、Li 2.22 ZrCl 5.89 (PO 4 ) 0.11 、Li 2.24 ZrCl 5.88 (PO 4 ) 0.12 、Li 2.3 ZrCl 5.85 (PO 4 ) 0.15 、Li 2.4 ZrCl 5.8 (PO 4 ) 0.2 、Li 2.6 ZrCl 5.7 (PO 4 ) 0.3 Or Li (lithium) 2.1 ZrCl 5.95 (PS 4 ) 0.05 。
Method for preparing solid ion conductor compound
According to another aspect, a method of preparing a solid ion conductor compound may include: providing a mixture comprising: a halide compound containing an M element, a halide compound including an M 'element, and a compound including a Z anion, wherein the M element is at least one alkali metal, the M' element is at least one of a divalent metal, a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal, and the Z anion is at least one of a trivalent anion; and treating the mixture in a solid phase to produce the solid ion conductor compound. Here, the solid ion conductor compound may be the aforementioned solid ion conductor compound.
The halide compound containing an element M may include a lithium halide. For example, the lithium halide may include at least one of LiF, liCl, liBr, or LiI. For example, the lithium halide may include at least one of LiCl or LiBr.
The halide compound containing an M 'element may be a divalent, trivalent, tetravalent, pentavalent, or hexavalent metal halide, and for example, the halide compound containing an M' element may include zirconium halides and yttrium halides. For example, the zirconium halide can include ZrF 4 、ZrCl 4 、ZrBr 4 Or ZrI 4 And yttrium halide may comprise YF 3 、YCl 3 、YBr 3 Or YI 3 At least one of (a) and (b). For example, the zirconium halide may include ZrCl 4 Or ZrBr 4 And yttrium halide may comprise YCl 3 Or YBR 3 At least one of (a) and (b).
The Z anion containing compound may include a lithium precursor compound that contains a trivalent anion. For example, the Z anion containing compound may include Li 3 PO 4 、Li 3 (C 6 H 5 O 7 )、Li 3 PS 4 、Li 3 [Fe(CN)]、Li 3 [Ag(S 2 O 3 ) 2 ]、Li 3 N, or Li 3 At least one of P.
According to embodiments, the halide compound containing an M element and the halide compound containing an M' element may be mixed in a stoichiometric ratio of about 1.8:1 or more and less than about 2:1. For example, the halide compound containing an M element and the halide compound containing an M' element may be mixed in a stoichiometric ratio of about 1.8:1 to about 1.99:1, about 1.8:1 to about 1.98:1, about 1.8:1 to about 1.97:1, about 1.8:1 to about 1.96:1, or about 1.8:1 to about 1.95:1, but the embodiment is not limited thereto.
According to an embodiment, treating the mixture in a solid phase to obtain the solid ion conductor compound may include ball milling the mixture in a dry and inert atmosphere at about 400 revolutions per minute (rpm) for about 48 hours. The dry and inert atmosphere may be an Ar atmosphere or a nitrogen atmosphere.
According to an embodiment, the ball milling may be performed for a first period of time and then with a rest period of time. Here, the first segment and the rest segment may be the same or different from each other. For example, the first segment may be twice the time of the rest segment or, for example, three times or more. Thus, by having the rest segment during the ball milling, a solid ion conductor compound having improved ion conductivity can be obtained.
According to embodiments, the first segment may be in the range of about 10 minutes to about 20 minutes. For example, the first period may be about 12 minutes to about 18 minutes, or about 15 minutes.
According to embodiments, the rest period may be in the range of about 3 minutes to about 10 minutes. For example, the rest period may be in the range of about 3 minutes to about 7 minutes, or about 5 minutes. In one aspect, ball-milling mixing is performed for a first period of time, and the ball-milling mixing further includes a rest period of time after the first period of time, wherein the first period of time and the rest period of time are repeated.
According to embodiments, the method of preparing the solid ion conductor compound may be performed at room temperature and may not include calcination or crystallization. For example, the preparation of the solid ion conductor compound may be carried out at room temperature (e.g., 25 ℃).
The method of preparing the solid ion conductor compound may include crystallization by heat treatment after mixing the raw materials, however, in the disclosure, the method of preparing the solid ion conductor compound may not include separate crystallization after mixing the solid phases. In one aspect, a separate crystallization step is omitted. Therefore, the preparation method is simplified and deformation of the material structure due to calcination can be prevented. Thus, a solid ion conductor compound having improved ionic conductivity and having a desired composition and crystalline structure can be obtained.
The inert atmosphere is an atmosphere containing inert gas. Examples of the inert gas include nitrogen and argon. However, the embodiment is not limited thereto. Any suitable inert gas available in the art may be used.
Electrochemical cell
According to an embodiment, an electrochemical cell may include: a positive electrode layer including a positive electrode active material; a negative electrode layer including a negative electrode active material; and a solid electrolyte layer between the positive electrode layer and the negative electrode layer and including a solid electrolyte, wherein at least one of the positive electrode layer or the solid electrolyte layer may include the solid ion conductor compound described above. By including the solid ion conductor compound in the electrochemical cell, the lithium ion conductivity and chemical stability of the electrochemical cell are improved.
The electrochemical cell may be, for example, an all-solid secondary battery, a secondary battery containing a liquid electrolyte, or a lithium air battery. However, the embodiment is not limited thereto. Any suitable electrochemical cell useful in the art may be used.
The all-solid secondary battery will be described in further detail as an example.
All-solid-state secondary battery: of the first type
The all-solid secondary battery may include the solid ion conductor compound. For example, the all-solid secondary battery may include: a positive electrode layer including a positive electrode active material; a negative electrode layer including a negative electrode active material; and a solid electrolyte layer between the positive electrode layer and the negative electrode layer and including a solid electrolyte, wherein at least one of the positive electrode active material layer or the solid electrolyte layer may include the solid ion conductor compound described above.
The all-solid secondary battery according to the embodiment may be prepared as follows.
Solid electrolyte layer
First, a solid electrolyte layer may be prepared. The solid electrolyte layer may be prepared by mixing and drying the above-described solid ion conductor compound and binder, or by rolling a powder of the solid ion conductor compound represented by formula 1 in a specific (specific) form under a pressure of about 1 ton to about 10 tons. The solid ion conductor compound is useful as a solid electrolyte.
The average diameter of the solid electrolyte may be, for example, in the range of about 0.5 micrometers (μm) to about 20 μm. By having such an average diameter of the solid electrolyte, the binding property is improved during formation of the calcined body, and the ion conductivity and lifetime characteristics of the solid electrolyte particles can be improved.
The thickness of the solid electrolyte layer may be in the range of about 10 μm to about 200 μm. By having such a thickness of the solid electrolyte layer, sufficient lithium ion mobility can be ensured, and as a result, high ion conductivity can be obtained.
In addition to the aforementioned solid ion conductor compounds, the solid electrolyte layer may further include a solid electrolyte such as a sulfide-based (i.e., sulfide) solid electrolyte and/or an oxide-based (i.e., oxide) solid electrolyte.
The sulfide-based solid electrolyte in the related art may include, for example, at least one of lithium sulfide, silicon sulfide, phosphorus sulfide, or boron sulfide. The sulfide-based solid electrolyte may include Li 2 S、P 2 S 5 、SiS 2 、GeS 2 Or B 2 S 3 At least one of (a) and (b). The sulfide-based solid electrolyte particles in the related art may be Li 2 S or P 2 S 5 . The sulfide-based solid electrolyte may have a higher lithium ion conductivity than other inorganic compounds. For example, the sulfide-based solid electrolyte may include Li 2 S and P 2 S 5 . When the sulfide solid electrolyte material included in the sulfide-based solid electrolyte includes Li 2 S-P 2 S 5 When Li 2 S vs P 2 S 5 May for example be in the range of about 50:50 to about 90:10. In addition, li can be 3 PO 4 Halogen, halogen compound, li 2+2x Zn 1-x GeO 4 (“LISICON” 3+y 4-x x ；0<x<1)、LiPON (“LIPON”；-3<y<3，0<x<4)、Li 3.25 Ge 0.25 P 0.75 S 4 ("Thio-LISICON"), or Li 2 O-Al 2 O 3 -TiO 2 -P 2 O 5 ("LATP") is added to the sulfide-based solid electrolyte such as Li 2 S-P 2 S 5 、SiS 2 、GeS 2 Or B 2 S 3 To prepare an inorganic solid electrolyte. The inorganic solid electrolyte may be used as a sulfide solid electrolyte in the related art. Non-limiting examples of sulfide solid electrolyte materials in the relevant field may include: li (Li) 2 S-P 2 S 5 ；Li 2 S-P 2 S 5 LiX (wherein X is a halogen element); li (Li) 2 S-P 2 S 5 -Li 2 O；Li 2 S-P 2 S 5 -Li 2 O-LiI；Li 2 S-SiS 2 ；Li 2 S-SiS 2 -LiI；Li 2 S-SiS 2 -LiBr；Li 2 S-SiS 2 -LiCl；Li 2 S-SiS 2 -B 2 S 3 -LiI；Li 2 S-SiS 2 -P 2 S 5 -LiI；Li 2 S-B 2 S 3 ；Li 2 S-P 2 S 5 -Z m S n (wherein m and n may each be positive numbers, and Z may be Ge, zn, or Ga); li (Li) 2 S-GeS 2 ；Li 2 S-SiS 2 -Li 3 PO 4 The method comprises the steps of carrying out a first treatment on the surface of the And Li (lithium) 2 S-SiS 2 -Li p MO q (where p and q may each be positive numbers, and M may be P, si, ge, B, al, ga, or In). In this regard, the sulfide-based solid electrolyte material may be prepared by: treatment of starting materials of sulfide-based solid electrolyte materials by melt quenching methods, or mechanical grinding methods(e.g. Li 2 S or P 2 S 5 ). Further, calcination may be performed after the above treatment.
The binder included in the solid electrolyte layer may be, for example, styrene Butadiene Rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, or polyvinyl alcohol. However, the embodiment is not limited thereto. Any suitable binder useful in the art may be used. The binder of the solid electrolyte layer may be the same as or different from the binder of the positive electrode layer or the negative electrode layer.
Positive electrode layer
Next, the positive electrode layer was prepared. The positive electrode layer may be prepared by forming a positive electrode active material layer including a positive electrode active material on a current collector. The average diameter of the positive electrode active material may be, for example, about 2 μm to about 10 μm.
The positive electrode active material may be any suitable positive electrode active material usable in the art for use in a secondary battery. For example, the positive electrode active material may be a lithium transition metal oxide, or a transition metal sulfide. For example, the positive electrode active material may be at least one of cobalt, manganese, or a composite oxide of nickel metal and lithium.
Examples of the positive electrode active material may include a compound represented by at least one of: li (Li) a A 1-b B 1 b D 1 2 (wherein 0.90.ltoreq.a.ltoreq.1.8 and 0.ltoreq.b.ltoreq.0.5); li (Li) a E 1-b B 1 b O 2-c D 1 c (wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05); liE 2-b B 1 b O 4-c D 1 c (wherein b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05); li (Li) a Ni 1-b-c Co b B 1 c D 1 α (wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0)<α≤2)；Li a Ni 1-b-c Co b B 1 c O 2-α F 1 α (wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0)<α<2)；Li a Ni 1-b-c Co b B 1 c O 2-α F 1 2 (wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0)<α<2)；Li a Ni 1-b-c Mn b B 1 c D 1 α (wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0)<α≤2)；Li a Ni 1-b-c Mn b B 1 c O 2-α F 1 α (wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0) <α<2)；Li a Ni 1-b- c Mn b B 1 c O 2-α F 1 2 (wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0)<α<2)；Li a Ni b E c G d O 2 (wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, and d is more than or equal to 0.001 and less than or equal to 0.1); li (Li) a Ni b Co c Mn d G e O 2 (wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, d is more than or equal to 0 and less than or equal to 0.5, and e is more than or equal to 0.001 and less than or equal to 0.1); li (Li) a NiG b O 2 (wherein 0.90.ltoreq.a.ltoreq.1.8 and 0.001.ltoreq.b.ltoreq.0.1); li (Li) a CoG b O 2 (wherein 0.90.ltoreq.a.ltoreq.1.8 and 0.001.ltoreq.b.ltoreq.0.1); li (Li) a MnG b O 2 (wherein 0.90.ltoreq.a.ltoreq.1.8 and 0.001.ltoreq.b.ltoreq.0.1); li (Li) a Mn 2 G b O 4 (wherein 0.90.ltoreq.a.ltoreq.1.8 and 0.001.ltoreq.b.ltoreq.0.1); QO (quality of service) 2 ；QS 2 ；LiQS 2 ；V 2 O 5 ；LiV 2 O 2 ；LiI 1 O 2 ；LiNiVO 4 ；Li (3-f) J 2 (PO 4 ) 3 (wherein f is more than or equal to 0 and less than or equal to 2); li (Li) (3-f) Fe 2 (PO 4 ) 3 (wherein f is more than or equal to 0 and less than or equal to 2); or LiFePO 4 . In the foregoing formula, a may be at least one of nickel (Ni), cobalt (Co), or manganese (Mn); b (B) 1 At least one of aluminum (Al), ni, co, mn, chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), or rare earth elements; d (D) 1 May be at least one of oxygen (O), fluorine (F), sulfur (S), or phosphorus (P); e may be at least one of Co or Mn; f (F) 1 May be at least one of F, S, or P; g canAl, cr, mn, fe, mg, lanthanum (La), cerium (Ce), sr, or V; q may be at least one of titanium (Ti), molybdenum (Mo), or Mn; i 1 At least one of Cr, V, fe, scandium (Sc), or yttrium (Y); and J may be V, cr, mn, co, ni, or at least one of copper (Cu). For example, the positive electrode active material may be LiCoO 2 、LiMn x O 2x (where x=1 or 2), liNi 1- x Mn x O 2 (wherein 0<x<1)、LiNi 1-x-y Co x Mn y O 2 (wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.5), liNi 1-x-y Co x Al y O 2 (wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.5), liFePO 4 、TiS 2 、FeS 2 、TiS 3 Or Fe 2 S 3 。
A compound having a coating layer added to one of these compounds may also be used, and a mixture of these compounds and a compound having a coating layer added thereto may also be used. In embodiments, the coating added on the surface of these compounds may include at least one coating element compound as follows: oxides, hydroxides, oxyhydroxides, oxycarbonates, or hydroxycarbonates of the coating elements. In embodiments, these compounds of the coating may be amorphous or crystalline. In an embodiment, the coating element included in the coating layer may be magnesium (Mg), aluminum (Al), cobalt (Co), potassium (K), sodium (Na), calcium (Ca), silicon (Si), titanium (Ti), vanadium (V), tin (Sn), germanium (Ge), gallium (Ga), boron (B), arsenic (As), zirconium (Zr), or a mixture thereof. The method of forming the coating layer may be selected within a range that does not affect the physical properties of the positive electrode active material. The coating method may be, for example, a spraying method or a dipping method. A detailed description of the coating method is omitted herein because the method is easily understood by one of ordinary skill in the art.
The positive electrode active material may include a lithium salt of a transition metal oxide having a layered rock salt structure, for example, among lithium transition metal oxides. The term "layered rock salt type structure" as used herein refers to the structure: wherein the atomic layers of oxygen and metal alternateAnd arranged regularly in a cubic rock salt-type structure<111>The directional and corresponding atomic layers thus form a two-dimensional plane. The term "cubic rock salt type structure" as used herein refers to a NaCl type structure, which is one of crystal structures, in which face-centered cubic lattices formed of anions and cations, respectively, are offset by half of the ridges of each unit cell (unit cell). Examples of the lithium transition metal oxide having a layered rock salt type structure may be a ternary lithium transition metal oxide represented by: liNi x Co y Al z O 2 (NCA) wherein 0<x<1，0<y<1，0<z<1, and x+y+z=1, or LiNi x’ Co y’ Mn z’ O 2 (NCM) wherein 0<x’<1，0<y’<1，0<z’<1, and x ' +y ' +z ' =1. When the positive electrode active material includes a ternary lithium transition metal oxide having a layered rock-salt type structure, the all-solid secondary battery 1 may have further improved energy density and thermal stability.
According to an embodiment, the positive electrode layer may include a material consisting of LiNi x Co y Al z O 2 Or LiNi x' Co y' Mn z' O 2 Represented as positive electrode active material, wherein 0<x<1，0<y<1，0<z<1, and x+y+z=1 and 0<x'<1，0<y'<1，0<z'<1, x ' +y ' +z ' =1, a part or all of the surface of the positive electrode active material may be coated with the solid ion conductor compound, and in addition, a known lithium ion conductor compound such as Li may be further coated thereon 2 ZrO 3 Or Li (lithium) 2 O-ZrO 2 (LZO) compounds.
For example, when the positive electrode active material includes nickel (Ni) as a ternary lithium transition metal oxide such as NCA or NCM, the capacity density of the all-solid secondary battery may be increased, thereby allowing for a reduction in metal elution of the positive electrode active material upon charging. Accordingly, the all-solid secondary battery may have improved cycle characteristics.
The positive electrode active material may be, for example, in a particle shape, such as a sphere shape or an ellipsoid shape. The particle diameter of the positive electrode active material is not particularly limited. The diameter may be in a range applicable to a positive electrode active material of an all-solid secondary battery in the related art. The content of the positive electrode active material of the positive electrode layer is not particularly limited. The content may be within a range applicable to a positive electrode layer of an all-solid secondary battery in the related art. In the positive electrode active material layer, the content of the positive electrode active material may be, for example, in the range of about 50 weight percent (wt%) to about 95 wt%.
The positive electrode active material layer may further include the solid ion conductor compound.
The positive electrode active material layer may include a binder. Examples of the binder may include, for example, styrene Butadiene Rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, or polyethylene.
The positive electrode active material layer may include a conductive agent. Examples of the conductive agent include graphite, carbon black, carbon Nanotubes (CNF), acetylene black, ketjen black, carbon fibers, or metal powder.
The positive electrode active material layer may further include additives such as a filler, a coating agent, a dispersing agent, and an ion-conducting auxiliary agent, in addition to the positive electrode active material, the solid ion conductor, the binder, or the conductive agent.
Also, the filler, coating agent, dispersing agent, or ion-conducting auxiliary that may be included in the positive electrode active material layer may be any suitable material for an electrode in an all-solid secondary battery.
Examples of the positive electrode current collector include a plate or foil including aluminum (Al), indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), germanium (Ge), lithium (Li), or an alloy thereof. The positive electrode current collector may be omitted.
The positive electrode current collector may further include a carbon layer disposed on one or both sides of the metal substrate. By additionally providing a carbon layer on the metal substrate, it is possible to prevent the metal of the metal substrate from being corroded by the solid electrolyte included in the positive electrode layer and to reduce the interfacial resistance between the positive electrode active material layer and the positive electrode current collector. The thickness of the carbon layer may be, for example, about 1 μm to about 5 μm. When the thickness of the carbon layer is too thin, it may be difficult to completely block the contact between the metal substrate and the solid electrolyte. When the thickness of the carbon layer is too thick, the energy density of the all-solid secondary battery may be reduced. The carbon layer may include amorphous carbon or crystalline carbon.
Negative electrode layer
Next, the anode layer was prepared. The negative electrode layer may be manufactured in the same manner as the positive electrode layer, except that a negative electrode active material is used instead of the positive electrode active material. The anode layer may be prepared by forming an anode active material layer including the anode active material on an anode current collector.
The anode active material layer may further include the solid ion conductor compound. The negative active material may be at least one of lithium metal or a lithium metal alloy. The anode active material layer may further include an anode active material in the related art in addition to at least one of the lithium metal or the lithium metal alloy. The anode active material in the related art may include, for example, at least one of the following: metals capable of alloying with lithium, transition metal oxides, non-transition metal oxides, or carbonaceous materials. Examples of the metal capable of alloying with lithium include gold (Au), silver (Ag), silicon (Si), tin (Sn), aluminum (Al), germanium (Ge), lead (Pb), bismuth (Bi), antimony (Sb), si-Y alloy (where Y is at least one of an alkali metal, an alkaline earth metal, a group 13 element, a group 14 element, a group 15 element, a group 16 element, a transition metal, or a rare earth element, and Y is not Si), or Sn-Y alloy (where Y is at least one of an alkali metal, an alkaline earth metal, a group 13 element, a group 14 element, a group 15 element, a group 16 element, a transition metal, or a rare earth element, and Y is not Sn). Y may be at least one of: magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), (Rf), vanadium (V), niobium (Nb), tantalum (Ta), and +.>(Db), chromium (Cr), molybdenum (Mo), tungsten (W), and->(Sg), technetium (Tc), rhenium (Re)>(Bh), iron (Fe), lead (Pb), ruthenium (Ru), osmium (Os),>(Hs), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), boron (B), aluminum (Al), gallium (Ga), tin (Sn), indium (In), thallium (Tl), germanium (Ge), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), sulfur (S), selenium (Se), tellurium (Te), or polonium (Po). For example, the transition metal oxide may be lithium titanium oxide, vanadium oxide, or lithium vanadium oxide. The non-transition metal oxide may be, for example, snO 2 Or SiO x (wherein 0<x<2). Examples of the carbonaceous material may include crystalline carbon, amorphous carbon, and mixtures thereof. Examples of the crystalline carbon may include graphite such as natural graphite or artificial graphite, which is in the form of unshaped, plate, flake, sphere, or fiber. Examples of the amorphous carbon may include soft carbon (carbon sintered at low temperature), hard carbon, mesophase pitch carbide, and sintered coke. />
As shown in fig. 7, the all-solid secondary battery 1 according to the embodiment may include a solid electrolyte layer 30, a positive electrode layer 10 on one surface of the solid electrolyte layer 30, and a negative electrode layer 20 on the other surface of the solid electrolyte layer 30. The positive electrode layer 10 may include a positive electrode active material layer 12 in contact with the solid electrolyte layer 30 and a positive electrode current collector 11 in contact with the positive electrode active material layer 12, and the negative electrode layer 20 may include a negative electrode active material layer 22 in contact with the solid electrolyte layer 30 and a negative electrode current collector 21 in contact with the negative electrode active material layer 22. The all-solid secondary battery 1 can be completed by, for example, the following: a positive electrode active material layer 12 is provided on a first side of the solid electrolyte layer 30, and a negative electrode active material layer 22 is provided on a second side of the solid electrolyte layer 30, and a positive electrode current collector 11 and a negative electrode current collector 21 are provided on the positive electrode active material layer 12 and the negative electrode active material layer 22, respectively. In the embodiment, the all-solid secondary battery 1 can be completed by, for example, the following: a negative electrode active material layer 22, a solid electrolyte layer 30, a positive electrode active material layer 12, and a positive electrode current collector 11 are sequentially disposed on a negative electrode current collector 21.
The positive electrode layer and the solid electrolyte layer may be prepared in the same manner as in the manufacture of the all-solid secondary battery.
The anode layer 20 may include an anode current collector 21 and an anode active material layer 22 on the anode current collector 21, wherein the anode active material layer 22 may include, for example, an anode active material and a binder.
The anode active material included in the anode active material layer 22 may have, for example, a particle shape. The average particle diameter of the anode active material having a particle shape may be, for example, 4 μm or less, 3 μm or less, 2 μm or less, 1 μm or less, or 900nm or less. The average particle diameter of the anode active material having a particle shape may be, for example, about 10nm to about 4 μm, about 10nm to about 3 μm, about 10nm to about 2 μm, about 10nm to about 1 μm, or about 10nm to about 900nm. When the anode active material has an average particle diameter in any of these ranges, reversible absorption and/or desorption of lithium can be promoted upon charge and discharge of the battery. The average particle diameter of the anode active material may be, for example, a median diameter (D50) measured by a laser particle size analyzer.
The anode active material included in the anode active material layer 22 may include, for example, at least one of a carbonaceous anode active material, a metal or a metalloid anode active material.
The carbonaceous anode active material may be amorphous carbon. The amorphous carbon may be, for example, carbon Black (CB), acetylene Black (AB), furnace Black (FB), ketjen Black (KB), or graphene. But the embodiment is not limited thereto. Any suitable amorphous carbon used in the art may be used. Amorphous carbon is carbon with no crystallinity or very low crystallinity, and is distinguished from crystalline carbon or graphite-based (i.e., graphitic) carbon.
The metal or metalloid anode active material may be gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), or zinc (Zn), but the embodiment is not limited thereto. Any suitable metal or metalloid anode active material available in the art capable of forming an alloy or compound with lithium may be used. For example, nickel (Ni) does not alloy with lithium and is therefore not a metal anode active material.
The anode active material layer 22 may include the aforementioned anode active material or may include a mixture of a plurality of different anode active materials. For example, the anode active material layer 22 may include only amorphous carbon or at least one of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), or zinc (Zn). For example, the anode active material layer 22 may include a mixture of amorphous carbon and at least one of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), or zinc (Zn). The mixing ratio of amorphous carbon to gold, etc. may be in a weight ratio, for example, in the range of about 10:1 to about 1:2, about 5:1 to about 1:1, or about 4:1 to about 2:1, but the embodiments are not limited thereto. The ratio may be selected according to desired characteristics of the all-solid secondary battery 1. Since the anode active material layer may have such a composition, the cycle characteristics of the all-solid secondary battery 1 may be further improved.
The anode active material included in the anode active material layer 22 may include a mixture of first particles of amorphous carbon and second particles of a metal or metalloid, for example. Examples of the metal or metalloid may include gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), or zinc (Zn). In embodiments, the metalloid may be a semiconductor. The second particles may be present in an amount ranging from about 8 wt% to about 60 wt%, from about 10 wt% to about 50 wt%, from about 15 wt% to about 40 wt%, or from about 20 wt% to about 30 wt%, based on the total weight of the mixture. When the second particles have a content within any of these ranges, for example, the cycle characteristics of the all-solid secondary battery 1 may be further improved.
The binder included in the anode active material layer 22 may be, for example, styrene-butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, vinylidene fluoride/hexafluoropropylene copolymer, polyacrylonitrile, or polymethyl methacrylate. However, the embodiment is not limited thereto. Any suitable binder useful in the art may be used. The binder may comprise a single or a plurality of different binders.
Since the anode active material layer 22 includes the binder, the anode active material layer 22 may be stabilized on the anode current collector 21. In addition, cracks in the anode active material layer 22 may be suppressed, despite variations in the volume and/or relative position of the anode active material layer 22 during charge and discharge. For example, when the anode active material layer 22 does not include the binder, the anode active material layer 22 may be easily separated from the anode current collector 21. Since the anode active material layer 22 is separated from the anode current collector 21, in a portion in which the anode current collector 21 is exposed, the possibility of occurrence of a short circuit may increase due to contact of the anode current collector with the solid electrolyte layer 30. The anode active material layer 22 may be prepared by: a slurry in which the material of the anode active material layer 22 is dispersed is coated on the anode current collector 21, and the slurry is dried. By including the binder in the anode active material layer 22, the anode active material can be stably dispersed in the slurry. For example, when the slurry is applied to the anode current collector 21 by screen printing, clogging of the screen (for example, clogging due to agglomeration of the anode active material) can be prevented.
The anode active material layer 22 may further include additives such as a filler, a coating agent, a dispersing agent, or an ion-conducting auxiliary agent used in the related art in the all-solid secondary battery 1.
The thickness of the anode active material layer 22 may be, for example, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5% or less of the thickness of the cathode active material layer 12. The thickness of the anode active material layer 22 may be, for example, in the range of about 1 μm to about 20 μm, about 2 μm to about 10 μm, or about 3 μm to about 7 μm. When the thickness of the anode active material layer 22 is too thin, lithium dendrites formed between the anode active material layer 22 and the anode current collector 21 may collapse the anode active material layer 22, so that the cycle characteristics of the all-solid secondary battery 1 are not improved. When the thickness of the anode active material layer 22 is too thick, the all-solid secondary battery 1 may have deteriorated energy density and increased internal resistance through the anode active material layer 22, so that the cycle characteristics of the all-solid secondary battery 1 are not improved.
When the thickness of the anode active material layer 22 is reduced, for example, the charge capacity of the anode active material layer 22 may also be reduced. The charge capacity of the anode active material layer 22 may be, for example, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, 5% or less, or 2% or less of the charge capacity of the cathode active material layer 12. The charge capacity of the anode active material layer 22 may be, for example, in the range of about 0.1% to about 50%, about 0.1% to about 40%, about 0.1% to about 30%, about 0.1% to about 20%, about 0.1% to about 10%, about 0.1% to about 5%, or about 0.1% to about 2% of the charge capacity of the cathode active material layer 12. When the charge capacity of the anode active material layer 22 is too small, the thickness of the anode active material layer 22 may be too thin, and lithium dendrites between the anode active material layer 22 and the anode current collector 21 may collapse the anode active material layer 22 during repeated charge and discharge, so that the cycle characteristics of the all-solid secondary battery 1 are not improved. When the charge capacity of the anode active material layer 22 is too large, the all-solid secondary battery 1 may have deteriorated energy density and increased internal resistance through the anode active material layer 22, so that the cycle characteristics of the all-solid secondary battery 1 are not improved.
The charge capacity of the positive electrode active material layer 12 may be obtained by multiplying the specific charge capacity (milliamp-hours per gram, mAh/g) of the positive electrode active material by the mass of the positive electrode active material in the positive electrode active material layer 12. When a plurality of positive electrode active materials are used, a specific charge capacity x mass value for the corresponding positive electrode active material can be obtained. The sum of these values may be the charge capacity of the positive electrode active material layer 12. The charge capacity of the anode active material layer 22 can also be calculated in the same manner. The charge capacity of the anode active material layer 22 may be obtained by multiplying the specific charge capacity (mAh/g) of the anode active material by the mass of the anode active material in the anode active material layer 22. When a plurality of anode active materials are used, a specific charge capacity x mass value for the corresponding anode active material can be obtained. The sum of these values may be the charge capacity of the anode active material layer 22. Here, the specific charge capacity of the positive electrode active material and the specific charge capacity of the negative electrode active material are each a capacity evaluated using an all-solid half-cell in which lithium metal is used as a counter electrode. By measuring the charge capacity using the all-solid half battery, the charge capacities of the positive electrode active material layer 12 and the negative electrode active material layer 22 can be directly measured. When the corresponding charge capacity obtained is divided by the mass of each active material, a specific charge capacity can be obtained. The charge capacity of the positive electrode active material layer 12 and the charge capacity of the negative electrode active material layer 22 may each be an initial charge capacity measured at the 1 st charge cycle.
All-solid-state secondary battery: of the second type
As shown in fig. 8, the all-solid secondary battery 1a may include, for example: a positive electrode layer 10 including a positive electrode active material layer 12 on a positive electrode current collector 11; a negative electrode layer 20 including a negative electrode active material layer 22 on a negative electrode current collector 21; and an electrolyte layer 30 between the positive electrode layer 10 and the negative electrode layer 20, wherein the positive electrode active material layer 12 and/or the electrolyte layer 30 may include the solid ion conductor compound described above. The all-solid secondary battery 1a may further include a metal layer 23, for example, between the anode current collector 21 and the anode active material layer 22. The metal layer 23 may include lithium or a lithium alloy.
The all-solid secondary battery according to the embodiment may be prepared as follows. The positive electrode layer and the solid electrolyte layer may be prepared in the same manner as in the manufacture of the all-solid secondary battery. As shown in fig. 8, in the all-solid secondary battery 1a, the metal layer 23 may be located between the anode current collector 21 and the anode active material layer 22, for example, before the all-solid secondary battery 1a is assembled, or the metal layer 23 may be precipitated between the anode current collector 21 and the anode active material layer 22 by charging after the all-solid secondary battery 1a is assembled. When the metal layer 23 is located between the anode current collector 21 and the anode active material layer 22 before the all-solid secondary battery 1a is assembled, since the metal layer 23 is a metal layer including lithium, the metal layer 23 may serve as a lithium reservoir. For example, before the all-solid secondary battery 1a is assembled, a lithium foil may be located between the anode current collector 21 and the anode active material layer 22.
The metal layer 23 may include a lithium alloy. The lithium alloy may be, for example, a Li-Al alloy, a Li-Sn alloy, a Li-In alloy, a Li-Ag alloy, a Li-Au alloy, a Li-Zn alloy, a Li-Ge alloy, or a Li-Si alloy, but the embodiment is not limited thereto. Any suitable lithium alloy available in the art for use as a lithium alloy may be used. The metal layer 23 may comprise one of the alloys, lithium, or several types of alloys.
The thickness of the lithium alloy is not particularly limited, but may be, for example, in a range of about 1 μm to 1,000 μm, 1 μm to 500 μm, 1 μm to 200 μm, 1 μm to 150 μm, 1 μm to 100 μm, or 1 μm to 50 μm. When the thickness of the metal layer 23 is too thin, the metal layer 23 may be difficult to use as a lithium reservoir. When the thickness of the metal layer 23 is too thick, the mass and volume of the all-solid secondary battery 1a may increase, thereby deteriorating the cycle characteristics of the all-solid secondary battery 1 a. The metal layer 23 may be, for example, a metal foil having a thickness in this range.
The cycle characteristics of the all-solid secondary battery 1a including the metal layer can be further improved. When the metal layer 23 is precipitated by charging after the all-solid secondary battery 1a is assembled, the energy density of the all-solid secondary battery 1a may be increased because the all-solid secondary battery 1a does not include the metal layer 23 at the time of assembly. For example, when the all-solid secondary battery 1a is charged, charging may be performed exceeding the charge capacity of the anode active material layer 22. That is, the anode active material layer 22 may be overcharged. In the initial charge, the anode active material layer 22 may be intercalated with lithium. That is, the anode active material included in the anode active material layer 22 may form an alloy or a compound with lithium ions that have migrated from the cathode layer 10. When the charge exceeds the capacity of the anode active material layer 22, for example, lithium is precipitated at the back surface of the anode active material layer 22, that is, between the anode current collector 21 and the anode active material layer 22. The metal layer corresponding to the metal layer 23 may be formed by precipitated lithium. The metal layer 23 may be a metal layer mainly including lithium (i.e., lithium metal). These results are obtained, for example, when the anode active material included in the anode active material layer 22 includes a material that forms an alloy or compound with lithium. Upon discharge, lithium in the metal layers, i.e., the anode active material layer 22 and the metal layer 23, may be ionized and move toward the cathode layer 10. Therefore, lithium can be used as the anode active material in the all-solid secondary battery 1 a. Further, the anode active material layer 22 may cover the metal layer 23, so that the anode active material layer 22 may serve as a protective layer for the metal layer 23 and may suppress deposition and growth of dendrites. Therefore, short circuit and capacity deterioration of the all-solid secondary battery 1a can be suppressed, and as a result, the cycle characteristics of the all-solid secondary battery 1a can be improved. In addition, when the metal layer 23 is provided by charging after the all-solid secondary battery 1a is assembled, the region between the anode current collector 21 and the anode active material layer 22 may be, for example, a Li metal-free region that may not contain lithium (Li) metal in the initial state or after the discharge state of the all-solid secondary battery 1 a.
For example, negative electrode current collector 21 may include a material that is not reactive with lithium and does not form an alloy or compound with lithium. The material of the negative electrode current collector 21 may include, for example, copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), or nickel (Ni), but the embodiment is not limited thereto. Any suitable electrode current collector available in the art may be used. The negative electrode current collector 21 may include one type of the metals described above, or an alloy or cladding material of at least two metals. The negative electrode current collector 21 may be, for example, a plate shape or a foil shape.
The all-solid secondary battery 1a may further include a thin film (not shown) including an element capable of forming an alloy with lithium, for example, on the anode current collector 21. The thin film may be located between the anode current collector 21 and the anode active material layer 22. The film may include elements such as elements that can form an alloy with lithium. The element capable of forming an alloy with lithium may be, for example, gold, silver, zinc, tin, indium, silicon, aluminum, or bismuth, but is not necessarily limited thereto. Any suitable element that can form an alloy with lithium can be used. The film may comprise an alloy of one or more of these metals. By disposing the thin film on the anode current collector 21, for example, the deposition shape of the metal layer 23 deposited between the thin film and the anode active material layer 22 is further flattened, thereby further improving the cycle characteristics of the all-solid secondary battery 1 a.
The thickness of the film may be, for example, in the range of about 1 nanometer (nm) to about 800nm, about 10nm to about 700nm, about 50nm to about 600nm, or about 100nm to about 500 nm. When the thickness of the thin film is less than 1nm, it may be difficult to exhibit the function of the thin film. When the thickness of the thin film is too thick, the thin film itself intercalates lithium, and the amount of lithium deposited in the anode decreases, thereby decreasing the energy density of the all-solid battery and deteriorating the cycle characteristics of the all-solid secondary battery 1 a. The thin film may be provided on the anode current collector 21 by, for example, a vacuum deposition method, a sputtering method, or a plating method, but is not necessarily limited thereto. Any suitable method in the art capable of forming a thin film may be used.
Hereinafter, the inventive concept will be described in detail with reference to examples and comparative examples. These examples are for illustrative purposes only and are not intended to limit the scope of the inventive concept.
Examples
Preparation of solid ion conductor compounds
Example 1
ZrCl as a halide compound containing M' element in Ar atmosphere in a glove box 4 LiCl as halide compound containing M element, and Li as compound containing Z anion 3 (PO 4 ) To a planetary ball mill at a stoichiometric ratio of 1:1.95:0.05 followed by zirconia (YSZ) balls. Then, after pulverizing and mixing at 400rpm in an Ar atmosphere for 15 minutes, a cycle with a rest period of 5 minutes was repeated for 48 hours to obtain solid ion conductor compounds having compositions shown in table 1 below. Subsequently, the solid ion conductor compound obtained for X-ray diffraction (XRD) analysis was pressed at a uniaxial pressure of 350 megapascals (MPa) to prepare a wafer having a thickness of about 10 millimeters (mm) and a diameter of about 13 mm.
Example 2
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PO 4 ) Is 1:1.99:0.01, followed by pressing to prepare a wafer thereof.
Example 3
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PO 4 ) Is 1:1.98:0.02, followed by pressing to prepare a disc thereof.
Example 4
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PO 4 ) Is 1:1.96:0.04, followed by pressing to prepare a wafer thereof.
Example 5
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PO 4 ) Is 1:1.94:0.06, followed by pressing to prepare a disc thereof.
Example 6
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PO 4 ) Is 1:1.9:0.1, followed by pressing to prepare a wafer thereof.
Example 7
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 、LiCl、Li 3 (PO 4 ) And YCl 3 Is 0.8:1.95:0.05:0.2, followed by pressing to prepare a disc thereof.
Example 8
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 、LiCl、Li 3 (PO 4 ) And YCl 3 Is 0.5:1.95:0.05:0.5,followed by pressing to prepare a disc thereof.
Example 9
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PS 4 ) Is 1:1.95:0.05, followed by pressing to prepare a disc thereof.
Example 10
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PO 4 ) Is 1:1.89:0.11, followed by pressing to prepare a wafer thereof.
Example 11
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PO 4 ) Is 1:1.88:0.12, followed by pressing to prepare a wafer thereof.
Example 12
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PO 4 ) Is 1:1.85:0.15, followed by pressing to prepare a disc thereof.
Example 13
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PO 4 ) Is 1:1.8:0.2, followed by pressing to prepare a disc thereof.
Example 14
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PS 4 ) Is 1:1.7:0.3, followed by pressing to prepare a wafer thereof.
Comparative example 1
Solid ion conductor compounds having compositions as shown in table 1 were obtained in the same manner as in example 1, except that: zrCl as raw material 4 And LiCl in a stoichiometric ratio of 1:2, followed by pressing to prepare a wafer thereof.
Comparative example 2
Solid ion conductor compounds having compositions as shown in table 1 were obtained in the same manner as in example 1, except that: YCl as raw material 3 And LiCl in a stoichiometric ratio of 1:3, followed by pressing to prepare a wafer thereof.
Comparative example 3
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 2 The stoichiometric ratio of O was 1:1.95:0.05, followed by pressing to prepare a wafer thereof.
Comparative example 4
A solid ion conductor compound was obtained in the same manner as in example 1, except that: YCl 3 LiCl and Li 2 The stoichiometric ratio of O was 1:2.95:0.05, followed by pressing to prepare a wafer thereof.
Comparative example 5
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 2 (SO 4 ) Is 1:1.95:0.05, followed by pressing to prepare a disc thereof.
Comparative example 6
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and LiNO 3 Is 1:1.95:0.05, followed by pressing to prepare a disc thereof.
Comparative example 7
A solid ion conductor compound was obtained in the same manner as in example 1, except that: zrCl 4 LiCl and Li 3 (PO 4 ) Is 1:1.6:0.4, followed by pressing to prepare a disc thereof.
Preparation of all-solid secondary battery
Example 15
Preparation of the Positive electrode layer
As positive electrode active materialLiNi is used as a material 0.9 Co 0.05 Mn 0.05 O 2 (NCM) Li 2 ZrO 3 (LZO) coating to prepare LZO-NCM positive electrode active material. The solid ion conductor compound prepared in example 1 was crushed into a round piece as a solid electrolyte to prepare a powder. Carbon Nanofibers (CNF) were prepared as a conductive agent. The LZO-NCM positive electrode active material, the solid electrolyte, and the conductive agent were mixed at a weight ratio of 60:52:5 to prepare a positive electrode mixture.
The prepared positive electrode mixture was coated on a current collector, and the coated current collector was dried to prepare a positive electrode layer. Then, a positive electrode layer having a thickness of 50 μm and a diameter of 11mm was prepared by using a punch having a diameter of 11 mm.
Preparation of solid electrolyte
The solid ion conductor compound prepared in example 1 was pulverized by using an agate mortar, and the solid electrolyte powder was pressed at a uniaxial pressure of 200MPa to prepare a wafer of solid electrolyte having a thickness of about 500 μm and a diameter of about 13 mm.
In addition, a solid electrolyte Li available from Mitsui was prepared 6 PS 5 Cl。
Preparation of negative electrode layer
A metal lithium foil having a thickness of 20 μm was prepared as a negative electrode.
Preparation of all-solid secondary battery
Negative electrode layer, the Li 6 PS 5 The Cl solid electrolyte, the solid electrolyte prepared in example 1, and the positive electrode layer were sequentially stacked on a stainless steel (SUS) base electrode. Then, it was subjected to pressing at a pressure of 300MPa for 3 minutes by using a Cold Isostatic Press (CIP) machine, thereby preparing an all-solid secondary battery.
Comparative example 8
Preparation of the Positive electrode layer
As the positive electrode active material, liNi 0.9 Co 0.05 Mn 0.05 O 2 (NCM) Li 2 ZrO 3 (LZO) coating to prepare LZO-NCM positive electrode active material. The solid prepared in comparative example 1 was separated as a solid electrolyteThe discs of subconductor compounds are crushed to produce a powder. Carbon Nanofibers (CNF) were prepared as a conductive agent. The positive electrode active material, the solid electrolyte, and the conductive agent were mixed at a weight ratio of 60:52:5 to prepare a positive electrode mixture.
The prepared positive electrode mixture was coated on a current collector, and the coated current collector was dried to prepare a positive electrode layer. Then, a positive electrode layer having a thickness of 50 μm and a diameter of 11mm was prepared by using a punch having a diameter of 11 mm.
Preparation of solid electrolyte
The solid ion conductor compound prepared in comparative example 1 was pulverized by using an agate mortar, and the solid electrolyte powder was pressed at a uniaxial pressure of 200MPa to prepare a wafer of solid electrolyte having a thickness of about 500 μm and a diameter of about 13 mm.
In addition, li is prepared 6 PS 5 Cl solid electrolyte (Li available from Mitsui 6 PS 5 Cl)。
Preparation of negative electrode layer
A metal lithium foil having a thickness of 20 μm was prepared as a negative electrode.
Preparation of all-solid secondary battery
Negative electrode layer, li 6 PS 5 The Cl solid electrolyte, the solid electrolyte prepared in comparative example 1, and the positive electrode layer were sequentially stacked on the SUS base electrode. Then, it was subjected to pressing at a pressure of 300MPa by using a CIP machine for 3 minutes, thereby preparing an all-solid secondary battery.
Comparative example 9
Preparation of the Positive electrode layer
As the positive electrode active material, liNi 0.9 Co 0.05 Mn 0.05 O 2 (NCM) Li 2 ZrO 3 (LZO) coating to prepare LZO-NCM positive electrode active material. Preparation of a known solid electrolyte (Li available from Mitsui 6 PS 5 Cl) as a solid electrolyte. Carbon Nanofibers (CNF) were prepared as a conductive agent. The positive electrode active material, the solid electrolyte, and the conductive agent were mixed at a weight ratio of 60:30:5 to prepare a positive electrode mixture.
The prepared positive electrode mixture was coated on a current collector, and the coated current collector was dried to prepare a positive electrode layer. Then, a positive electrode layer having a thickness of 50 μm and a diameter of 11mm was prepared by using a punch having a diameter of 11 mm.
Preparation of solid electrolyte
Preparation of a known solid electrolyte (Li available from Mitsui 6 PS 5 Cl)。
Preparation of negative electrode layer
A metal lithium foil having a thickness of 20 μm was prepared as a negative electrode.
Preparation of all-solid secondary battery
Negative electrode layer, li 6 PS 5 A Cl solid electrolyte, and a positive electrode layer were sequentially stacked on the SUS base electrode. Then, it was subjected to pressing at a pressure of 300MPa by using a CIP machine for 3 minutes, thereby preparing an all-solid secondary battery.
Evaluation example 1: x-ray photoelectron spectroscopy (XPS) analysis
The solid ion conductor compound prepared in example 1 was pulverized by using an agate mortar to prepare a powder. XPS analysis was performed on the powder, and the results thereof are shown in fig. 9.
As shown in fig. 9, in the XPS plot, a peak from element "O" was observed at 534 electron volts (eV), which demonstrates PO 4 The presence of anions.
Evaluation example 2: x-ray diffraction analysis
The solid ion conductor compounds prepared in examples 1, 2, 4, 5 and 6 were pulverized by using an agate mortar to prepare powders, and XRD spectra of the powders were measured. The results are shown in FIG. 1. The variation of peak position and half width at the diffraction angle of 32.3 ° 2θ is shown in fig. 2. The calculated lattice constants of the crystalline structures are shown in fig. 3.
As shown in fig. 1 to 3, the solid ion conductor compounds of examples 1, 2, 4, 5 and 6 each include the same P3-m1 space group crystal structure, and are due to PO with lattice constant 4 3- The introduction of anions increases, and the lattice volume increases by about 0.4％。
Evaluation example 3: measurement of ion conductivity
The solid ion conductor compounds prepared in examples 1 to 6 and 10 to 14 and comparative example 1 were pulverized by using an agate mortar to prepare powders. The powder was mixed at a rate of 4 tons/cm (ton/cm 2 ) For 2 minutes to thereby prepare a wafer sample having a thickness of about 1mm and a diameter of about 13 mm. The prepared sample was sputtered with platinum (Pt) on both sides to form platinum (Pt) electrodes having a thickness of 10 μm and a diameter of 13mm disposed on both sides, thereby preparing a symmetrical battery. The preparation of the symmetrical cell was performed in a glove box in an Ar atmosphere.
The impedance of the wafer was measured by a two-probe method using an impedance analyzer (Material materials 7260 impedance analyzer) for a sample having platinum electrodes disposed on both sides. The frequency range is 1 hertz (Hz) to 1 megahertz (MHz) and the amplitude voltage is 10 millivolts (mV). The measurement was performed at a temperature of 25℃in an Ar atmosphere. Resistance values are obtained from arcs of Nyquist (Nyquist) diagrams for impedance measurement results, and ion conductivity is calculated in consideration of the area and thickness of the sample. The results of the measurement are shown in table 1.
Further, the change in ion conductivity according to the change in p value is shown in fig. 4.
Referring to table 1 and fig. 4, the examples in which trivalent anions were introduced showed significantly improved ion conductivity compared to the case in which trivalent anions were not substituted (comparative example 1) or monovalent or divalent anions were substituted (comparative examples 3 to 6). In addition, it was confirmed that the trivalent anion has improved ion conductivity in a range of more than 0 and 0.3 or less.
Evaluation example 4: cycle evaluation
The charge/discharge characteristics of the all-solid secondary batteries of example 15 and comparative example 8 were evaluated by the following charge/discharge test.
In the first cycle of the charge/discharge test at room temperature (25 ℃), charging was performed at a constant current of 0.1C until the battery voltage reached 4.2V, and charging was performed at a constant voltage of 4.2V until the current value reached 0.1C. Subsequently, the battery was discharged at a constant current of 0.1C until the battery voltage reached 2.5V. The C-rate is the discharge rate of the battery, and is obtained by dividing the total capacity of the battery by the total discharge period of 1 hour, for example, the C-rate for a battery having a discharge capacity of 1.6 ampere hour will be 1.6 ampere. The total capacity is determined by the discharge capacity at the first cycle. 0.1C or C/10 refers to the current that completely discharged the battery at 10 hours.
The initial efficiencies are shown in table 2. It was confirmed that the battery of example 15 exhibited excellent initial efficiency compared to that of comparative example 8.
TABLE 2
Initial efficiency
Example 15 99.8％
Comparative example 8 92.3％
After the initial efficiency evaluation, charging was performed at a constant current of 0.1C until the battery voltage reached 4.2V, and charging was performed at a constant voltage of 4.2V until the current value reached 0.1C. Subsequently, the battery was discharged at a constant current of 0.1C until the battery voltage reached 2.5V. The charge and discharge cycle was repeated 20 times. After measuring the capacity in each cycle, the results are shown in fig. 5.
As shown in fig. 5, the capacity of the battery of comparative example 8 gradually decreased, however, the coulombic efficiency of the all-solid battery of example 10 exceeded 99.8%, confirming that the capacity remained almost constant.
Evaluation example 5: rate characteristic evaluation
The rate characteristics of the all-solid secondary batteries of example 15 and comparative examples 8 and 9 were evaluated by the following tests.
At room temperature (25 ℃), charging was performed at a constant current of 0.1C until the battery voltage reached 4.2V, and charging was performed at a constant voltage of 4.2V until the current value reached 0.1C. Subsequently, the battery was discharged at a constant current of 0.1C until the battery voltage reached 2.5V.
Subsequently, the battery was charged at a constant current of 0.1C until the battery voltage reached 4.2V, and charged at a constant voltage of 4.2V until the current value reached 0.1C, and then discharged at a constant current of 0.33C until the battery voltage reached 2.5V.
Subsequently, the battery was charged at a constant current of 0.1C until the battery voltage reached 4.2V, and charged at a constant voltage of 4.2V until the current value reached 0.1C, and then discharged at a constant current of 0.5C until the battery voltage reached 2.5V.
Subsequently, the battery was charged at a constant current of 0.1C until the battery voltage reached 4.2V, and charged at a constant voltage of 4.2V until the current value reached 0.1C, and then discharged at a constant current of 1C until the battery voltage reached 2.5V.
The specific capacity change of the all-solid batteries according to example 15 and comparative examples 8 and 9, in which the magnification was changed, is shown in fig. 6.
Referring to fig. 6, it was confirmed that the all-solid battery of example 10 exhibited a capacity retention of 43% at a rate of 1C.
As is apparent from the foregoing description, an electrochemical cell with improved cycling characteristics is provided by including a solid ion conductor compound with improved lithium ion conductivity.
It should be understood that the embodiments described herein should be considered in descriptive sense only and not for purposes of limitation. The descriptions of features or aspects in various embodiments should typically be considered as available for other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.

Claims (20)

1. A solid ion conductor compound comprising a compound represented by formula 1:
1 (1)
M 3+m+(l-1)o+2p (M' k+ ) n X 3+m+kn-lo-3p+q T l- o Z 3- p
Wherein, in the formula 1,
m is at least one alkali metal, and the alkali metal,
m' is at least one of a divalent metal, a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal,
x is at least one halogen, and the halogen is at least one halogen,
t is at least one of a monovalent anion or a divalent anion,
z is at least one of trivalent anions,
k is more than or equal to 2 and less than or equal to 6, l is more than or equal to 1 and less than or equal to 2, m is more than or equal to 3 and less than or equal to 3, n is more than or equal to 0 and less than or equal to 1, o is more than or equal to 0 and less than or equal to 3, p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 3 and less than or equal to 0 (3+m+kn-lo-3p+q).
2. The solid ion conductor compound of claim 1, wherein M comprises at least one of Li, na, K, rb, or Cs.
3. The solid ion conductor compound of claim 1, wherein M' comprises at least one of Mg, zn, ca, sr, ba, eu, Y, gd, in, er, la, yb, ce, ho, sn, th, nb, mo, W, sb, bi, zr, hf, ti, or Si.
4. The solid ion conductor compound of claim 1, wherein X comprises at least one of F, cl, br, or I.
5. The solid ion conductor compound of claim 1, wherein Z comprises PO 4 3- 、(C 6 H 5 O 7 ) 3- 、PS 4 3- 、[Fe(CN)] 3- 、[Ag(S 2 O 3 ) 2 ] 3- 、N 3- Or P 3- At least one of (a) and (b).
6. The solid ion conductor compound of claim 1, wherein T comprises NO 3 - 、CH 3 COO - 、OH - 、HCO 3 - 、CrO 4 2- 、SO 4 2- 、CO 3 2- Or BH 4 - At least one of (a) and (b).
7. The solid ion conductor compound of claim 1, wherein formula 1 is represented by formula 2:
2, 2
(Li 1-h M h ) 3+m+(l-1)o+2p (M' k+ ) n X 3+m+kn-lo-3p+q T l- o ((PO 4 ) 1-i Z' i ) p
Wherein, in the formula 2,
m is at least one alkali metal different from Li,
z' is different from PO 4 3- At least one of the trivalent anions of (c) is used,
m' is at least one of a divalent metal, a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal,
x is at least one halogen, and the halogen is at least one halogen,
t is at least one of a monovalent anion or a divalent anion, and
k is more than or equal to 2 and less than or equal to 6, l is more than or equal to 1 and less than or equal to 2, m is more than or equal to 3, n is more than or equal to 0 and less than or equal to 1, o is more than or equal to 0 and less than or equal to 3, p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 3,0< (3+m+kn-lo-3p+q), h is more than or equal to 0 and less than or equal to 1.
8. The solid ion conductor compound of claim 1, wherein formula 1 is represented by formula 3:
3
(Li 1-h M h ) 3+m+(l-1)o+2p ((Zr) 1-j M' j k+ ) n X 3+m+kn-lo-3p+q T l- o ((PO 4 ) 1-i Z' i ) p
Wherein, in the formula 3,
m is at least one alkali metal different from Li,
z' is different from PO 4 3- At least one of the trivalent anions of (c) is used,
m' is at least one of a divalent metal, a trivalent metal, a tetravalent metal, a pentavalent metal, and a hexavalent metal different from Zr,
x is at least one halogen, and the halogen is at least one halogen,
t is at least one of a monovalent anion or a divalent anion, and
k is more than or equal to 2 and less than or equal to 6, l is more than or equal to 1 and less than or equal to 2, m is more than or equal to 3, n is more than or equal to 0 and less than or equal to 1, o is more than or equal to 0 and less than or equal to 3, p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 3,0< (3+m+kn-lo-3p+q), h is more than or equal to 0 and less than or equal to 1, i is more than or equal to 0 and less than or equal to j is more than or equal to 1.
9. The solid ion conductor compound of claim 1, wherein the solid ion conductor compound has diffraction peaks at diffraction angles of 16 °2Θ ± 0.5 °2Θ, 20 °2Θ ± 0.5 °2Θ, 30 °2Θ ± 0.5 °2Θ, 32 °2Θ ± 0.5 °2Θ, 42 °2Θ ± 0.5 °2Θ, and 50 °2Θ ± 0.5 °2Θ when analyzed by X-ray diffraction using cukα radiation.
10. The solid ion conductor compound according to claim 1, wherein 0<p.ltoreq.0.3 in formula 1.
11. The solid ion conductor compound of claim 1, wherein the solid ion conductor compound comprises at least one of a crystalline phase and an amorphous phase.
12. The solid ion conductor compound of claim 1, wherein the solid ion conductor compound comprises crystals belonging to the P3-m1 space group.
13. The solid ion conductor compound of claim 1, wherein the solid ion conductor compound has a and c lattice constants that are greater than the a and c lattice constants of a solid ion conductor compound that does not include a trivalent anion represented by Z.
14. The solid ion conductor compound of claim 1, wherein the solid ion conductor compound is Li 2.1 ZrCl 5.95 (PO 4 ) 0.05 、Li 2.02 ZrCl 5.99 (PO 4 ) 0.01 、Li 2.04 ZrCl 5.98 (PO 4 ) 0.02 、Li 2.08 ZrCl 5.96 (PO 4 ) 0.04 、Li 2.12 ZrCl 5.94 (PO 4 ) 0.06 、Li 2.2 ZrCl 5.9 (PO 4 ) 0.1 、Li 2.15 Zr 0.8 Y 0.2 Cl 5.95 (PO 4 ) 0.05 、Li 2.45 Zr 0.5 Y 0.5 Cl 5.95 (PO 4 ) 0.05 、Li 2.22 ZrCl 5.89 (PO 4 ) 0.11 、Li 2.24 ZrCl 5.88 (PO 4 ) 0.12 、Li 2.3 ZrCl 5.85 (PO 4 ) 0.15 、Li 2.4 ZrCl 5.8 (PO 4 ) 0.2 、Li 2.6 ZrCl 5.7 (PO 4 ) 0.3 Or Li (lithium) 2.1 ZrCl 5.95 (PS 4 ) 0.05 。
15. A method of preparing the solid ion conductor compound of any of claims 1-14, the method comprising:
Providing a mixture comprising: a halide compound comprising an element M, a halide compound comprising an element M ', and a compound comprising a Z anion, wherein the element M is at least one alkali metal, the element M' is at least one of a divalent metal, a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal, and the Z anion is at least one of a trivalent anion; and
the mixture is treated in a solid phase to produce the solid ion conductor compound.
16. The method of claim 15, wherein treating the mixture in a solid phase to produce the solid ion conductor compound comprises ball milling the mixture under a dry and inert atmosphere.
17. The method of claim 16, wherein the ball milling is performed for a first period of time, and the ball milling further comprises a rest period of time after the first period of time, wherein the first period of time and the rest period of time are repeated.
18. An electrochemical cell comprising:
a positive electrode layer including a positive electrode active material;
a negative electrode layer including a negative electrode active material; and
A solid electrolyte layer between the positive electrode layer and the negative electrode layer and including a solid electrolyte,
wherein at least one of the positive electrode layer or the solid electrolyte layer comprises the solid ion conductor compound according to any one of claims 1 to 14.
19. The electrochemical cell of claim 18, wherein the electrochemical cell is an all-solid secondary battery,
the solid electrolyte layer includes a sulfide solid electrolyte,
the positive electrode active material layer includes at least one of positive electrode active materials represented by: liNi x Co y Al z O 2 Wherein 0 is<x<1，0<y<1，0<z<1, and x+y+z=1; or LiNi x' Co y' Mn z' O 2 Wherein 0 is<x'<1，0<y'<1，0<z'<1, and x ' +y ' +z ' =1, and
the negative electrode active material layer includes lithium metal.
20. The electrochemical cell of claim 18, wherein the discharge capacity remains at about 93% or greater for up to 20 cycles compared to the initial discharge capacity when charged and discharged at 0.1C in the range of about 2.5 volts to about 4.2 volts.
CN202310879959.6A 2022-08-02 2023-07-18 Solid ion conductor compound, electrochemical cell and method for preparing solid ion conductor compound Pending CN117497833A (en)

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