# US 2016/0254530 A1 · Cathode materials for secondary (rechargeable) lithium batteries

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- Number: US 2016/0254530 A1
- Document ID: US20160254530A1
- Status: Published application
- Kind: A1
- Application number: 15/150,162
- Filed: 2016-05-09
- Published: 2016-09-01
- Earliest claimed: 1996-04-23
- Assignees: Hydro-Quebec
- Applicants: Hydro-Quebec
- Inventors: Michel Armand; John B. Goodenough; Akshaya K. Padhi; Kirakodu S. Nanjundaswamy; Christian Masquelier
- Web page: https://patentgrep.com/patent/US20160254530A1

## CPC

- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- C01B 25/45: containing plural metal, or metal and ammonium
- G02F 1/155: Electrodes
- H01M 4/049: {Manufacturing of an active layer by chemical means}
- H01M 4/1397: of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 4/622: {being polymers}
- H01M 4/625: {Carbon or graphite}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 4/583: Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 10/052: Li-accumulators
- H01M 2004/028: {Positive electrodes}
- H01M 2300/0068: inorganic
- Y02E 60/10: Energy storage using batteries
- Y10T 29/49108: Electric battery cell making
- 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}
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The invention relates to materials for use as electrodes in an alkali-ion secondary (rechargeable) battery, particularly a lithium-ion battery. The invention provides transition-metal compounds having the ordered-olivine or the rhombohedral NASICON structure and the polyanion (PO4)3− as at least one constituent for use as electrode material for alkali-ion rechargeable batteries.

## Claims

### Claim 1

A cathode material for a rechargeable electrochemical cell, said cell also comprising an anode and an electrolyte, the cathode material comprising a compound having the formula LiMPO4, where M is at least one first-row transition-metal cation.

### Claim 2 (depends on 1)

The cathode material of claim 1, where M is further defined as being selected from the group consisting of Mn, Fe, Co, and Ni

### Claim 3 (depends on 1)

The cathode material of claim 1, where M is further defined as being a combination of cations, at least one of which is selected from the group consisting of Mn, Fe, Co and Ni.

### Claim 4 (depends on 3)

The cathode material of claim 3, where M is Fe1−xMnx or Fe1−xTix and 0<x<1.

### Claim 5 (depends on 2)

The cathode material of claim 2, wherein the cathode material has the formula LiFePO4.

### Claim 6

A cathode material for a rechargeable electrochemical cell, said cell also comprising an anode and an electrolyte, the cathode material comprising a rhombohedral NASICON material having the formula YxM2(PO4)3, where M is at least one first-row transition-metal cation and 0≦x≦5 and Y is Li or Na.

### Claim 7 (depends on 5)

The cathode material of claim 5, where M is selected from the group consisting of Fe, V, Mn, and Ti.

### Claim 8 (depends on 7)

The cathode material of claim 7, wherein the cathode material has the formula Li3+xFe2(PO4)3, where 0≦x≦2.

### Claim 9 (depends on 7)

The cathode material of claim 7, wherein the cathode material has the formula Li3Fe2(PO4)3.

### Claim 10 (depends on 7)

The cathode material of claim 7, having the formula Li1+xTix(PO4)3.

### Claim 11 (depends on 7)

The cathode material of claim 7, having it formula Li3FeTi(PO4)3.

### Claim 12 (depends on 7)

The cathode material of claim 7, having the formula LixTiNb(PO4)3, where 0≦x≦2.

### Claim 13 (depends on 7)

The cathode material of claim 7, having the formula Li1+xFeNb(PO4)3, where 0≦x≦2.

### Claim 14 (depends on 7)

The cathode material of claim 7, prepared by the process comprising the steps:
(a) preparing Na2Fe2(PO4)3; and
(b) contacting said Na2Fe2(PO4)3 with a molten lithium salt, such that an ionic exchange reaction occurs.

### Claim 15 (depends on 7)

The cathode material of claim 7, prepared by a direct solid state reaction.

### Claim 16

A cathode material for a rechargeable electrochemical cell, said cell also comprising an anode and an electrolyte, the cathode material comprising a rhombohedral NASICON material having the formula YyM2(PO4)y(XO4)3−y, where 0<y≦3, M is a transition-metal atom, 0≦x≦5, Y is Li or Na, and X=Si, As, or S.

### Claim 17 (depends on 16)

The cathode material of claim 16, wherein the cathode material has the formula Li1+xFe2(SO4)2(PO4), where 0≦x≦2.

### Claim 18 (depends on 17)

The cathode material of claim 17, prepared by the process comprising the steps:
(a) preparing an aqueous solution comprising FeCl3, (NH4)3SO4, and LiH2PO4;
(b) evaporating the solution to obtain dry material; and
(c) heating the dry material to about 500° C.

### Claim 19

A cathode material for a rechargeable electrochemical cell also comprising an anode and an electrolyte, the cathode comprising a rhombohedral NASICON material having the formula A3−xV2(PO4)3, where A may be Li, Na or a combination thereof and 0≦x≦2.

### Claim 20 (depends on 19)

The cathode material of claim 19, wherein the cathode material has the formula Li2−xNaVx(PO4)3, where 0≦x≦2.

### Claim 21 (depends on 19)

The cathode material of claim 19, prepared by the process comprising the steps:
(a) preparing Na3V2(PO4)3; and
(b) contacting said Na3V2(PO4)3 with a molten salt, such that an ionic exchange reaction occurs.

### Claim 22 (depends on 19)

The cathode material of claim 19, prepared by a direct solid-state reaction.

### Claim 23

A cathode material for a rechargeable electrochemical cell, said cell also comprising an anode and an electrolyte, the cathode material comprising a compound having the formula:
Lix+yM1−(y+d+t+q+r)DdTtQqRr[PO4]1−(p+s+v)[SO4]p[SiO4]s[VO4]v
where:
M may be Fe2+ or Mn2+ or mixtures thereof;
D is a metal in the +2 oxidation state selected from the group consisting of: Mg2+, Ni2+, Co2+, Zn2+, Cu2+, and Ti2+;
T is a metal in the +3 oxidation state selected from the group consisting of: Al3+, Ti3+, Cr3+, Fe3+, Mn3+, Ga3+, Zn3+, and V3+;
Q is a metal in the +4 oxidation state selected from the group consisting of: Ti4+, Ge4+, Sn4+, and V4+;
R is a metal in the +5 oxidation state selected from the group consisting of: V5+, Nb5+, and Ta5+;
0≦x≦1;
0≦y, d, t, q, r, p, s, v≦1 wherein at least one of y, d, t, q, r, p, s, and v differ from 0 and
y+d+t+q+r≦1;
p+s+v≦1; and
3+s·p=x−y+t+2q+3r;
where x is the degree of intercalation during operation of the electrode material, y represents the fraction of lithium ions on the initial Fe2+ sites; d represents the fraction of divalent ions (noted as D) on the initial Fe2+ sites; t represents the fraction of trivalent ions (noted as T) on the initial Fe2+ sites; q represents the fraction of tetravalent ions (noted as Q) on the initial Fe2+ sites; r represents the fraction of pentavalent ions (noted as R) on the initial Fe2+ sites; p represents the fraction of hexavalent sulfur (as discrete SO42− tetrahedra) on the initial P5+ sites; s represents the fraction of tetravalent silicon (as discrete SiO42− tetrahedra) on the initial P5+ sites; and v represents the fraction of pentavalent vanadium ions on the initial P5+ sites, and M, D, T, Q and R reside in octahedral sites.

### Claim 24

A secondary battery comprising an anode, a cathode and an electrolyte, said cathode comprising an ordered olivine compound having the formula LiMPO4, where M is at least one first-row transition-metal cation.

### Claim 25 (depends on 23)

The battery of claim 23, where M is further defined as being selected from the group consisting of Mn, Fe, Co, and Ni.

### Claim 26 (depends on 23)

The battery of claim 23, where M is further defined as being a combination of cations, at least one of said cations being selected from the group consisting of Mn, Fe, Co, and Ni.

### Claim 27 (depends on 25)

The battery of claim 25, where M is Fe1−xMnx or Fe1−xTix, where 0≦x≦1.

### Claim 28 (depends on 23)

A secondary battery comprising an anode, a cathode and an electrolyte, said cathode comprising a modified olivine compound as set forth in claim 23.

### Claim 29 (depends on 28)

The battery of claim 28, wherein the anode comprises a compound selected from the group consisting of a metallic lithium, a lithium alloy, a lithium-carbon intercalation compound, a lithium-transition metal mixed nitride of antifluorite and lithium-titanium spinel having the formula Li1+xTi2−xO4 where 0≦x≦1/3 and 0≦z≦1−2x.

### Claim 30 (depends on 29)

The battery of claim 29, wherein said cathode further comprises a conducive additive.

### Claim 31 (depends on 30)

The battery of claim 30, wherein said conductive additive is carbon.

### Claim 32 (depends on 29)

The battery of claim 29, wherein said cathode further comprises an intercalation material with fast diffusion kinetics.

### Claim 33 (depends on 32)

The battery of claim 32, wherein said intercalation material is selected from the group consisting of a lamellar dichalcogenide, a vanadium oxide having the formula VOx where 2.1≦x≦2.5, and a NASICON-related material.

### Claim 34 (depends on 33)

The battery of claim 33, wherein said NASICON-related material is selected from the group consisting of Li3Fe2(PO4)3 and Li3−xFe2−xTix(PO4)3.

### Claim 35 (depends on 29)

The battery of claim 29, wherein said cathode further comprises a polymeric binder.

### Claim 36 (depends on 35)

The battery of claim 35, wherein said polymeric binder is selected from the group consisting of a homopolymer of tetrafluoroethylene, a copolymer of tetrafluoroethylene, an ethylene-propylene-diene terpolymer, a polyether, a polyester, a methylmethacrylate-based polymer, an acrylonitrile-based polymer, and a vinylidene fluoride-based polymer.

### Claim 37 (depends on 36)

The battery of claim 36, wherein said polymeric binder is a polyether.

### Claim 38 (depends on 37)

The battery of claim 37, wherein said polyether further comprises a salt comprising Li+ cations.

### Claim 39 (depends on 38)

The battery of claim 38, wherein said polyether is crosslinked.

### Claim 40 (depends on 35)

The battery of claim 35, wherein said polymeric binder has an ionic conductivity of between about 10−7 and about 10−2 (Scm−1).

### Claim 41 (depends on 38)

The battery of claim 38, wherein said polymeric binder is swollen by an aprotic solvent.

### Claim 42 (depends on 41)

The battery of claim 41, wherein said aprotic solvent is selected from the group consisting of: ethylene carbonate, propylene carbonate, dimethylcarbonate, diethylcarbonate, methyl-ethylcarbonate, γ-butyrolactone, a tetraalkylsulfamide, a diallylether of an ethylene glycol having a molecular weight ≦2000.

### Claim 43 (depends on 42)

The battery of claim 42, wherein said aprotic solvent is a diallylether of an ethylene glycol having a molecular weight ≦2000.

### Claim 44 (depends on 43)

The battery of claim 43, wherein said diallylether comprises a mono-ethylene glycol.

### Claim 45 (depends on 43)

The battery of claim 43, wherein said diallylether comprises a di-ethylene glycol.

### Claim 46 (depends on 43)

The battery of claim 43, wherein said diallylether comprise a tri-ethylene glycol.

### Claim 47 (depends on 43)

The battery of claim 43, wherein said diallylether comprises a tetra-ethylene glycol.

### Claim 48 (depends on 43)

The battery of claim 43, wherein said diallylether comprises an oligo-ethylene glycol higher than a tetra-ethylene glycol.

### Claim 49 (depends on 42)

The battery of claim 42, wherein said diallylether comprises a mixture of mono-, di-, tri-, tetra-, and higher oligo-ethylene glycols.

### Claim 50

A secondary battery comprising an anode, a cathode and an electrolyte, said cathode comprising a rhombohedral NASICON material having the formula YxM2(PO4)3, where M is at least one first-row transition-metal cation and 0≦x≦5 and Y is Li or Na, other than Li2+xFeTi(PO4)3.

### Claim 51 (depends on 27)

The battery of claim 27, where M is selected from the group comprising of Fe, V, Mn, and Ti.

### Claim 52 (depends on 28)

The battery of claim 28, wherein the cathode material has the formula LixFe2(PO4)3, where 0≦x≦2.

### Claim 53 (depends on 29)

The battery of claim 29, wherein the cathode material has the formula Li3Fe2(PO4)3.

### Claim 54 (depends on 28)

The battery of claim 28, wherein the cathode material has the formula Li2FeTi(PO4)3.

### Claim 55 (depends on 28)

The battery of claim 28, wherein the cathode material has the formula LixTiNb(PO4)3, where 0≦x≦2.

### Claim 56 (depends on 28)

The battery of claim 28, wherein the cathode material has the formula Li1+xFeNb(PO4)3, 0≦x≦2.

### Claim 57

A secondary battery comprising an anode, a cathode and an electrolyte, said cathode comprising a rhombohedral NASICON material having the formula YyM2(PO4)y(XO4)3−y, where 0<y≦3, M is a transition-metal atom 0≦x≦5, Y is Li or Na, and X=Si, As, or S.

### Claim 58 (depends on 34)

The battery of claim 34, wherein said cathode material has the formula Li1+x Fe2(PO4)(SO4)2, wherein 0≦x≦2.

### Claim 59

A secondary battery comprising an anode, a cathode and an electrolyte said cathode comprising a rhombohedral NASICON material having the formula A3−xV2(PO4)x, where A may be Li, Na or a combination thereof and 0≦x≦2.

### Claim 60 (depends on 36)

The battery of claim 36, wherein the cathode material has the formula Li3−xNaV2(PO4)3, where 0≦x≦2.

### Claim 61 (depends on 23)

A variable optical transmission device comprising transparent semi-conductor coated glass or plastic, and including at least one positive electrode and at least one negative electrode separated by a solid or gel electrolyte, wherein at least one electrode comprises a modified olivine compound as set forth in claim 23.