Source: https://patents.google.com/patent/US7955733
Timestamp: 2018-02-18 01:44:31
Document Index: 54660830

Matched Legal Cases: ['§ 1', '§ 1', '§ 1', '§ 1', '§ 1', '§ 1', '§ 1']

US7955733B2 - Cathode materials for secondary (rechargeable) lithium batteries - Google Patents
US7955733B2
US7955733B2 US12859865 US85986510A US7955733B2 US 7955733 B2 US7955733 B2 US 7955733B2 US 12859865 US12859865 US 12859865 US 85986510 A US85986510 A US 85986510A US 7955733 B2 US7955733 B2 US 7955733B2
US12859865
US20100314577A1 (en )
Preferred formulas for the ordered olivine electrode compounds of the invention include, but are not limited to LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, and mixed transition-metal compounds such as Li1-2xFe1−xTixPO4 or LiFe1−xMnxPO4, where 0<x<1. However, it will be understood by one of skill in the art that other compounds having the general formula LiMPO4 and an ordered olivine structure are included within the scope of the invention.
In another aspect, the invention provides electrode materials for a rechargeable electrochemical cell comprising an anode, a cathode and an electrolyte, with or without an electrode separator, where the electrode materials comprise a rhombohedral NASICON material having the formula YxM2 (PO4)3, where 0≦x≦5. Preferably, the compounds of the invention will be useful as the cathode of a rechargeable electrochemical cell. The alkali ion Y may be inserted from the electrolyte of the battery to the interstitial space of the rhombohedral M2 (XO4)3 NASICON host framework as the transition-metal M cation (or combination of cations) is reduced by charge-compensating electrons supplied by the external circuit of the battery during discharge with the reverse process occurring during charge of the battery. While it is contemplated that the materials of the invention may consist of either a single rhombohedral phase or two phases, e.g. orthorhombic and monoclinic, the materials are preferably single-phase rhombohedral NASICON compounds. Generally, M will be at least one first-row transition-metal cation and Y will be Li or Na. In preferred compounds, M will be Fe, V, Mn, or Ti and Y will be Li.
Preferred formulas for the rhombohedral NASICON electrode compounds of the invention include, but are not limited to those having the formula Li3+xFe2 (PO4)3, Li2+xFeTi (PO4)3, LixTiNb (PO4)3, and Li1+xFeNb (PO4)3, where 0<x<2. It will be understood by one of skill in the art that Na may be substituted for Li in any of the above compounds to provide cathode materials for a Na ion rechargeable battery. For example, one may employ Na3+xFe2 (PO4)3, Na2+xFeTi (PO4)3, NaxTiNb (PO4)3 or Na1+xFeNb (PO4)3, where 0<x<2, in a Na ion rechargeable battery. In this aspect, Na+ is the working ion and the anode and electrolyte comprise a Na compound.
In another aspect of the invention, the rhombohedral NASICON electrode compounds may have the general formula YxM2(PO4)y(XO4)3-y, where 0<y≦3, M is a transition-metal atom, Y is Li or Na, and X=Si, As, or S and acts as a counter cation in the rhombohedral NASICON framework structure. In this aspect, the compound comprises a phosphate anion as at least part of an electrode material. In preferred embodiments, the compounds are used in the cathode of a rechargeable battery. Preferred compounds having this general formula include, but are not limited to Li1+xFe2(SO4)2(PO4), where 0≦x≦1.
In a further embodiment, the invention provides electrode materials for a rechargeable electrochemical cell comprising an anode, a cathode and an electrolyte, with or without an electrode separator, where the electrode materials have a rhombohedral NASICON structure with the general formula A3+xV2(PO4)3. In these compounds, A may be Li, Na or a combination thereof and 0≦x≦2. In preferred embodiments, the compounds are a single-phase rhombohedral NASICON material. Preferred formulas for the rhombohedral NASICON electrode compounds having the general formula A3−xV2(PO4)3 include, but are not limited to those having the formula Li2−xNaV2(PO4)3, where 0≦x≦2.
FIGS. 6A and 6B. FIG. 6A shows discharge/charge curves vs. lithium at 0.1 mA·cm−2 for rhombohedral Li3+xFe2(PO4)3 where 0<x<2. The shape of the curve for lithium insertion into rhombohedral Li3−xFe2(PO4)3 is surprisingly different from that for the monoclinic form. However, the average Voc at 2.8 V remains the same. The Li+-ion distribution in the interstitial space appears to vary continuously with x with a high degree of disorder. FIG. 6B shows discharge/charge curves vs. lithium at 0.1 mA·cm−2 for monoclinic Li3+xFe2(PO4)3 where 0<x<2.
Pmax=ImaxVmax (5)
σLi=(B/T) exp (−E v /kT) (8)
Rin˜A/Ain (9)
dV/dI−R e1 +R c(A)+R c(C) (11)
The inventors compared redox energies in isostructural sulfates with phosphates to obtain the magnitude of the change due to the different inductive effects of sulfur and phosphorus. Rhombohedral Li1+xTi2 (PO4)3 has been shown to exhibit a flat open-circuit voltage Voc=2.5 V vs. lithium, which is roughly 0.8 V below the Ti4+/Ti3+ level found for FeTi(SO4)3. The flat voltage V(x) is indicative of a two-phase process. A coexistence of rhombohedral and orthorhombic phases was found for x=0.5 (Delmas and Nadiri 1988; Wang and Hwu 1992). Li2+xFeTi(PO4)3 of the present invention remains single phase on discharge.
All three phosphates Li3M2(PO4)3, where M=Fe, Fe/V, or V, have the monoclinic Fe2(SO4)3 structure if prepared by solid-state reaction. The inventors have found that these compounds exhibit a rhombohedral structure when prepared by ion exchange in LiNO3 at 300° C. from the sodium analog Na3Fe2(PO4)3. The discharge/charge curve of FIG. 6A for lithium insertion into rhombohedral Li3+xFe2(PO4)3 exhibits an average Voc of 2.8 V. This is surprisingly different from the curves for the monoclinic form (See FIG. 6B). The inventors have found that up to two lithiums per formula unit can be inserted into Li3Fe2(PO4)3, leading to Li5Fe2(PO4)3. The Li+-ion distribution in the interstitial space of Li3+xFe2 (PO4)3, where 0<x<2, appears to vary continuously with x with a high degree of disorder. FIG. 7A shows a reversible capacity loss on increasing the current density from 0.05 to 0.5 mA·cm−2. A reversible discharge capacity of 95 mAh·g−1 is still observed for rhombohedral Li3+xFe2(PO4)3 at a current density of 20 mA·g−1. This is much reduced compared to what is encountered with the monoclinic system (See FIG. 7B). With a current density of 23 mA·g−1 (or 1 mA·cm−2), the initial capacity of 95 mAh·g−1 was maintained in a coin cell up to the 40th cycle.
Rhombohedral LiFeNb(PO4)3 and Li2FeTi(PO4)3 can be prepared by ion exchange with molten LiNO3 at about 300° C. from NaFeNb (PO4)3 and Na2FeTi (PO4)3, respectively. Two Li atoms per formula unit can be inserted reversibly into Li2+xFeTi(PO4)3 with a little loss of capacity at 0.5 mA·cm−2. Insertion of the first Li atom in the range 2.7 V<V<3.0 V corresponds to the Fe3+/Fe2+ redox couple and of the second Li atom in the range of 2.5 V<V<2.7 V to an overlapping Ti4+/Ti3+ redox couple. The insertion of lithium into Li1+xFeNb(PO4)3 gives a V vs. x curve that further verifies the location of the relative positions of the Fe3+/Fe2+, Nb5+/Nb4+ redox energies in phosphates with NASICON-related structures. It is possible to insert three lithium atoms into the structure, and there are three distinct plateaus corresponding to Fe3+/Fe2+ at 2.8 V, Nb5+/Nb4+ at 2.2 V, and Nb4+/Nb5+ at 1.7 V vs. lithium in the discharge curve.
The rhombohedral A3−xV2(PO4)3 compounds of the invention can be prepared by ionic exchange from the monoclihnic sodium analog Na3V2(PO4)3. The inventors were also able to prepare the rhombohedral Li2NaV2 (PO4)3 with the NASICON framework by a direct solid-state reaction (FIG. 9). The discharge/charge curves at 0.05 mA·cm−2 (0.95 mA·g−1) for the rhombohedral LixNaV2(PO4)3 are shown in FIG. 8.
The rhombohedral LiFe2(SO4)2(PO4) may be prepared by obtaining an aqueous solution comprising FeCl3, (NH4)2SO4, and LiH2PO4, stirring the solution and evaporating it to dryness, and heating the resulting dry material to about 500° C. Discharge/charge curves vs. lithium at 0.1 mA·cm−2 for rhombohedral Li1+xFe2 (PO4)(SO4)2, where 0<x<3, are shown in FIG. 10.
1. A synthesized cathode material usable in a rechargeable electrochemical cell comprising one or more compounds, at least one of the compounds with an olivine structure comprising the general formula LiMPO4, where M is one first-row transition-metal selected from the group consisting of Fe, Mn, Ni and Ti.
2. The cathode material of claim 1, where M is Fe.
3. The cathode material of claim 1, where M is Mn.
4. The cathode material of claim 1, wherein the cathode material comprises a second compound.
5. A synthesized cathode material usable in a rechargeable electrochemical cell comprising one or more compounds, at least one of the compounds with an olivine structure comprising the general formula LiMPO4, where M is a combination of first-row transition-metals selected from the group consisting of Mn, Fe, Ti and Ni.
6. The cathode material of claim 5, where M is a combination of first row transition-metals selected from the group consisting of Mn, Fe and Ti and where Fe1−xMnx or Fe1−xTix and 0<x<1.
8. The cathode material of claim 5, wherein the cathode material comprises a second compound.
9. A synthesized cathode material usable in a rechargeable electrochemical cell comprising one or more compounds, at least one of the compounds with an olivine structure comprising the general formula LiMPO4, where M is one or more first-row transition-metals selected from the group consisting of Fe, Mn, Ni and Ti.
10. The cathode material of claim 9, wherein the cathode material comprises a second compound.
11. A secondary battery comprising a cathode comprising one or more compounds, at least one of the compounds with an olivine structure comprising the general formula LiMPO4, where M is one first-row transition-metal selected from the group consisting of Fe, Mn, Ni and Ti.
12. The battery of claim 11, where M is Fe.
13. The battery of claim 11, where M is Mn.
14. The battery of claim 11, the cathode further comprising a second compound.
15. A secondary battery comprising a cathode comprising one or more compounds, at least one of the compounds with an olivine structure comprising the general formula LiMPO4, where M is a combination of first-row transition-metals selected from the group consisting of Mn, Fe, Ti, and Ni.
16. The battery of claim 15, where M is a combination of first row transition-metals selected from the group consisting of Mn, Fe and Ti and where Fe1−xMnx or Fe1−xTix and 0<x<1.
17. The battery of claim 16, wherein the compound comprises the formula LiFe1−xMnxPO4 and 0<x<1.
18. The battery of claim 15, where M comprises a combination of cations of the same element selected from the group consisting of Mn, Fe, Ti and Ni.
19. The battery of claim 15, the cathode further comprising a second compound.
20. A secondary battery comprising a cathode comprising one or more compounds, at least one of the compounds with an olivine structure comprising the general formula LiMPO4, where M is one or more first-row transition-metals selected from the group consisting of Fe, Mn, Ni and Ti.
21. The battery of claim 20, the cathode further comprising a second compound.
US12859865 1996-04-23 2010-08-20 Cathode materials for secondary (rechargeable) lithium batteries Expired - Lifetime US7955733B2 (en)
US12859865 US7955733B2 (en) 1996-04-23 2010-08-20 Cathode materials for secondary (rechargeable) lithium batteries
US20100314577A1 true US20100314577A1 (en) 2010-12-16
US7955733B2 true US7955733B2 (en) 2011-06-07
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