# US 12,119,441 B2 · Solid ion conductor compound, solid electrolyte including solid ion conductor compound, electrochemical cell including solid ion conductor compound, and method of preparing solid ion conductor compound

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- Number: US 12,119,441 B2
- Document ID: US12119441B2
- Status: Granted
- Kind: B2
- Application number: 17/083,385
- Filed: 2020-10-29
- Published: 2021-05-06
- Granted: 2024-10-15
- Earliest claimed: 2019-11-01
- Assignees: Samsung SDI Co., Ltd.
- Applicants: Samsung SDI Co., Ltd.
- Inventors: Seoksoo Lee; Hyunseok Kim; Soyeon Kim
- Web page: https://patentgrep.com/patent/US12119441B2

## CPC

- H01M 10/0562: Solid materials
- C01B 25/14: Sulfur, selenium, or tellurium compounds of phosphorus
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/366: {as layered products}
- H01M 4/587: for inserting or intercalating light metals
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0585: of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
- H01M 10/4235: {Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence)}
- C01P 2002/30: Three-dimensional structures
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2006/40: Electric properties
- H01M 2004/027: {Negative electrodes}
- H01M 2300/0068: inorganic
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A compound represented by Formula 1 and having an argyrodite-type crystal structure: LixM1vPSyM2wM3z Formula 1 In Formula 1, M1 is at least one metal element of Group 1 to Group 15 of the periodic table, except Li, M2 is SOn, M3 is at least one element of Group 17 of the periodic table; and 4≤x≤8, 0≤v<1, 3≤y≤7, 0<w<2, 0≤z≤2, and 1.5≤n≤5.

## Claims

### Claim 1

A compound represented by Formula 1 and having an argyrodite-type crystal structure:
LixM1vPSyM2wM3z Formula 1
wherein, in Formula 1,
M1 comprises Ag, Cu, Fe, Zn, Cr, Sn, V, or a combination thereof,
M2 is SOn,
M3 is at least one element of Group 17 of the periodic table, and
4≤x≤8, 0<v<1, 3≤y≤7, 0<w<2, 0≤z≤2, and 1.5≤n≤5.

### Claim 2 (depends on 1)

The compound of claim 1, wherein 0≤v/(x+v)<0.2 and 0<w/(y+w)<0.2.

### Claim 3 (depends on 1)

The compound of claim 1, wherein the SOn is S4O6, S3O6, S2O3, S2O4, S2O5, S2O6, S2O7, S2O8, SO4, SO5, or a combination thereof.

### Claim 4 (depends on 1)

The compound of claim 1, wherein 0≤v/(x+v)<0.08 and 0<w/(y+w)<0.08.

### Claim 5 (depends on 1)

The compound of claim 1, wherein M1 comprises Mg, Ag, Cu, or a combination thereof.

### Claim 6 (depends on 1)

The compound of claim 1, wherein M3 comprises F, Cl, Br, I, or a combination thereof.

### Claim 7 (depends on 1)

The compound of claim 1, wherein the compound represented by Formula 1 is represented by Formula 2:
Li7-m-v-zM1vPS6-w-2M2wM3z Formula 2
wherein, in Formula 2,
M1 comprises Ag, Cu, Fe, Zn, Cr, Sn, V, or a combination thereof,
M2 is SOn,
M3 is at least one element of Group 17 of the periodic table, and
0<v<1, 0<w<2, 0≤z≤2, 1.5≤n≤5, and 1≤m≤2.

### Claim 8 (depends on 1)

The compound of claim 1, wherein the compound represented by Formula 1 is represented by one of Formula 3 or Formula 4:
(Li1-dM1d)aP(S1-eM2e)bM3c Formula 3
(Li1-dM1d)aLifcP(S1+fc-eM2e)b(M31-fM2f)c Formula 4
wherein, in Formulae 3 and 4,
M1 is Ag, Cu, Fe, Zn, Cr, Sn, V, or a combination thereof,
M2 is SO4,
M3 is at least one element of Group 17 of the periodic table;
5≤a≤7, 45b≤6, and 0≤c≤2, and
0<d≤0.08, 0<e≤0.08, 0<f≤0.08, and 0<e+f≤0.08.

### Claim 9 (depends on 1)

The compound of claim 1, wherein the compound represented by Formula 1 is represented by Formula 5 or Formula 6,
(Li1-dM1d)aP(S1-e(SO4)e)bM3c, or Formula 5
(Li1-dM1d)aLifcP(S1+fc-e(SO4)e)b(M31-f(SO4)f)c, Formula 6
wherein, in Formulae 5 and 6,
M1 is Ag, Cu, or a combination thereof;
M3 is at least one element of Group 17 of the periodic table;
5≤a≤7, 45b≤6, and 0≤c≤2, and
0<d<0.08, 0<<<0.08, 0<f<0.08, and 0<e+f<0.08.

### Claim 10

A compound represented by Formula 5d, Formula 5e, Formula 6a, Formula 6b, Formula 6c, Formula 6d, or Formula 6e, and having an argyrodite-type crystal structure:
(Li1-dAgd)aP(S1-e(SO4)e)bM3c, Formula 5d
(Li1-dCud)aP(S1-e(SO4)e)bM3c, Formula 5e
(Li1-dNad)aLifcP(S1+fc-e(SO4)e)b(M31-f(SO4)f)c, Formula 6a
(Li1-dKd)aLifcP(S1+fc-e(SO4)e)b(M31-f(SO4)f)c, Formula 6b
(Li1-dMgd)aLifcP(S1+fc-e(SO4)e)b(M31-f(SO4)f)c, Formula 6c
(Li1-dAgd)aLifcP(S1+fc-e(SO4)e)b(M31-f(SO4)f)c, or Formula 6d
(Li1-dCud)aLifcP(S1+fc-e(SO4)e)b(M31-f(SO4)f)c, Formula 6e
wherein, in Formula 5c, Formula 5d, Formula 5e, Formula 6a, Formula 6b, Formula 6c, Formula 6d, and Formula 6e,
each M3 is independently selected and is an element of Group 17 of the periodic table,
a, b, and c are each independently selected, and 5≤a≤7, 4≤b≤6, and 0≤c≤2, and
d, e, and f are each independently selected and 0<d<0.06, 0<e≤0.06, 0<f≤0.06, and 0<e+f≤0.06.

### Claim 11 (depends on 10)

The compound of claim 10, wherein the compound represented by Formula 1 is represented by:
(Li1-dCud)aP(S1-e(SO4)e)bFc, (Li1-dCud)aP(S1-e(SO4)e)bClc, (Li1-dCud)aP(S1-e(SO4)e)bBrc, (Li1-dCud)aP(S1-e(SO4)e)bIc,
(Li1-dCud)aLifcP(S1+fc-e(SO4)e)b(F1-f(SO4)f)c, (Li1-dCud)aLifcP(S1+fc-e(SO4)e)b(Cl1-f(SO4)f)c, (Li1-dCud)aLifcP(S1+fc-e(SO4)e)b(Br1-f(SO4)f)c, (Li1-dCud)aLifcP(S1+fc-e(SO4)e)b(I1-f(SO4)f)c,
(Li1-dMgd)aLifcP(S1+fc-e(SO4)e)b(F1-f(SO4)f)c, (Li1-dMgd)aLifcP(S1+fc-e(SO4)e)b(Cl1-f(SO4)f)c, (Li1-dMgd)aLifcP(S1+fc-e(SO4)e)b(Br1-f(SO4)f)c, (Li1-dMgd)aLifcP(S1+fc-e(SO4)e)b(I1-f(SO4)f)c,
(Li1-dAgd)aP(S1-e(SO4)e)bFc, (Li1-dAgd)aP(S1-e(SO4)e)bClc, (Li1-dAgd)aP(S1-e(SO4)e)bBrc, (Li1-dAgd)aP(S1-e(SO4)e)bIc,
(Li1-dAgd)aLifcP(S1+fc-e(SO4)e)b(F1-f(SO4)f)c, (Li1-dAgd)aLifcP(S1+fc-e(SO4)e)b(Cl1-f(SO4)f)c, (Li1-dAgd)aLifcP(S1+fc-e(SO4)e)b(Br1-f(SO4)f)c, or (Li1-dAgd)aLifcP(S1+fc-e(SO4)e)b(I1-f(SO4)f)c,
wherein, each a, b, c, d, e, and f is independently selected and 5≤a≤7, 4≤b≤6, 0≤c≤2, 0<d≤0.06, 0<e<0.06, 0<f<0.06, and 0<e+f<0.06.

### Claim 12

A compound represented by a formula of:
Lia+fcP(S1+fc-e(SO4)e)b(F1-f(SO4)f)c, Lia+fcP(S1+fc-e(SO4)e)b(Cl1-f(SO4)f)c, Lia+fcP(S1+fc-e(SO4)e)b(Br1-f(SO4)f)c, or Lia+fcP(S1+fc-e(SO4)e)b(I1-f(SO4)f)c,
wherein, in the formulae, 5≤a≤7, 4≤b≤6, and 0<c≤2; and 0<e<0.06, 0<f<0.06, and 0<e+f<0.06.

### Claim 13 (depends on 1)

The compound of claim 1, wherein the compound represented by Formula 1 has an ion conductivity of about 1 milliSiemens per centimeter or greater at a temperature of about 25° C.

### Claim 14 (depends on 1)

The compound of claim 1, wherein the compound represented by Formula 1 has an ion conductivity retention of about 70% or greater, when analyzed after 10 days in an air atmosphere having a dew point of less than −60° C.,
wherein the ion conductivity retention is defined as shown in Equation 1:
Ion conductivity retention=[Ion conductivity of the compound after 10 days/initial ion conductivity of the compound]×100%. Equation 1

### Claim 15 (depends on 1)

The compound of claim 1, wherein the compound represented by Formula 1 belongs to a cubic crystal system.

### Claim 16 (depends on 1)

The compound of claim 1, wherein the compound represented by Formula 1 belongs to a F-43m space group.

### Claim 17 (depends on 1)

The compound of claim 1, wherein the compound represented by Formula 1 has a first peak at a diffraction angle of 30.1°2θ+0.5°2θ and a second peak at a diffraction angle of 31.5°2θ+0.5°2θ, when analyzed by X-ray diffraction using a CuKα radiation, and
a compound having the same composition with that of the compound represented by Formula 1, except that M2 is S, has a third peak at a diffraction angle of 30.1°2θ+0.5°2θ and a fourth peak at a diffraction angle of 31.5°2θ+0.5°2θ when analyzed by X-ray diffraction using CuKα radiation, and
wherein the position of the first peak is at least 0.01°2θ less than the position of the third peak, and the position of the second peak is at least 0.01°2θ less than a position of the fourth peak.

### Claim 18 (depends on 1)

The compound of claim 1, wherein the compound represented by Formula 1 further has a peak corresponding to LiM3 at a diffraction angle of 35.0°2θ=1.0°2θ in when analyzed by X-ray diffraction using CuKα radiation.

### Claim 19 (depends on 1)

A protected cathode active material comprising:
a lithium transition metal oxide, a transition metal sulfide, a lithium transition metal sulfide, or a combination thereof; and
the compound of claim 1 on a surface of the lithium transition metal oxide, the transition metal sulfide, or the lithium transition metal sulfide.

### Claim 20 (depends on 1)

A solid electrolyte comprising the compound of claim 1.

### Claim 21 (depends on 1)

An electrochemical cell comprising:
a cathode layer comprising a cathode active material layer;
an anode layer comprising an anode active material layer; and
an electrolyte layer disposed between the cathode layer and the anode layer,
wherein at least one of the cathode active material layer and the electrolyte layer comprises the compound of claim 1.

### Claim 22 (depends on 21)

The electrochemical cell of claim 21, wherein the electrochemical cell is an all-solid secondary battery.

### Claim 23 (depends on 21)

The electrochemical cell of claim 21, wherein the anode active material layer comprises an anode active material and a binder, wherein the anode active material comprises amorphous carbon and Au, Pt, Pd, Si, Ag, Al, Bi, Sn, Zn, or a combination thereof.

### Claim 24 (depends on 21)

The electrochemical cell of claim 21, wherein the anode layer further comprises an anode current collector, and a metal layer is further comprised between the anode current collector and the anode active material layer, wherein the metal layer comprises lithium or a lithium alloy.

### Claim 25 (depends on 1)

A method of preparing the compound of claim 1, the method comprising:
contacting a compound comprising
lithium,
a compound comprising a metal element of Ag, Cu, Fe, Zn, Cr, Sn, V, or a combination thereof,
a compound comprising P,
a compound comprising SOn wherein 1.5≤n≤5, and
optionally a compound comprising a Group 17 element of the periodic table to prepare a mixture; and
heat-treating the mixture in an inert atmosphere to prepare the compound of claim 1.

### Claim 26 (depends on 25)

The method of claim 25, wherein the heat-treating comprises heat-treating at a temperature of about 400° C. to about 600° C. for about 1 hour to about 36 hours.