US2003190527A1PendingUtilityA1
Batteries comprising alkali-transition metal phosphates and preferred electrolytes
Priority: Apr 3, 2002Filed: Apr 3, 2002Published: Oct 9, 2003
Est. expiryApr 3, 2022(expired)· nominal 20-yr term from priority
H01M 4/5825H01M 4/582H01M 4/56H01M 10/0569H01M 4/5815H01M 4/622H01M 2004/027H01M 10/0525H01M 4/623H01M 4/624H01M 4/625H01M 10/0568H01M 4/0471H01M 4/136H01M 4/48H01M 4/58Y02E60/10
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Abstract
Lithium batteries comprising: (a) an electrode comprising a material of the formula A a M b (XY 4 ) c Z d , wherein (i) A is an alkaline metal and 0<a≦9; (ii) M comprises a transition metal, and 1≦b≦3; (iii) XY 4 is X′O 4-x Y′ x , X′O 4-y Y′ 2y , X″S 4 , or mixtures thereof, where X′ is P, As, Sb, Si, Ge, V, S, or mixtures thereof; X″ is P, As, Sb, Si, Ge, V, or mixtures thereof; Y′ is halogen, S, N, or mixtures thereof; 0≦x<3; and 0<y≦2; and 0<c≦3; and (iv) Z is OH, halogen, or mixtures thereof, and 0≦d≦6; and (b) a counter-electrode; and (c) an electrolyte comprising an alkyl and/or alkylene carbonate and a cyclic ester. Preferably, M additionally comprises at least one non-transition metal. Preferred embodiments include those having an olivine structure, where c=1, and those having a NASICON structure, where c=3.
Claims
exact text as granted — not AI-modifiedWhat is claimed is:
1 . A lithium battery comprising:
(a) a first electrode comprising an active material of the formula A a M b (XY 4 ) c Z d , wherein
(i) A is selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a ≦9;
(ii) M is one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 1≦b≦3;
(iii) XY 4 is selected from the group consisting of X′O 4-x Y′ x , X′O 4-y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; X″ is selected from the group consisting of P, As, Sb, Si, Ge, V and mixtures thereof; Y′ is selected from the group consisting of halogen, S, N, and mixtures thereof; 0≦x≦3; and 0<y≦2; and 0<c≦3;
(iv) Z is OH, halogen, or mixtures thereof, and 0≦d≦6; and
wherein M, XY 4 , Z, a, b, c, d, x and y are selected so as to maintain electroneutrality of said compound; (b) a second electrode which is a counter-electrode to said first electrode; and (c) an electrolyte comprising a mixture of a cyclic ester and a carbonate selected from the group consisting of alkyl carbonates, alkylene carbonates, and mixtures thereof.
2 . A battery according to claim 1 , wherein c is about 1.
3 . A battery according to claim 2 , wherein A comprises Li, and 0.1≦a≦2, and said active material has an olivine structure.
4 . A battery according to claim 1 , wherein c is about 3, and said active material has a NASICON structure.
5 . A battery according to claim 1 , wherein M comprises M′ 1-m M″ m , where M′ is at least one element from Groups 4 to 11 of the Periodic Table; M″ is at least one element from Groups 2, 3, and 12-16 of the Periodic Table; and 0<m<1.
6 . A battery according to claim 5 , wherein M′ is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.
7 . A battery according to claim 6 , wherein M′ is selected from the group consisting of Fe, Co, Mn, Ti, and mixtures thereof.
8 . A battery according to claim 5 , wherein M′ comprises Fe and Co.
9 . A battery according to claim 8 , wherein M″ is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.
10 . A battery according to claim 9 , wherein M″ is selected from the group consisting of Mg, Ca, Al, and mixtures thereof.
11 . A battery according to claim 1 , wherein X′ comprises Si or a mixture of Si and P, and X″ comprises Si or a mixture of Si and P.
12 . A battery according to claim 1 , wherein XY 4 is selected from the group consisting Of X′O 4-x Y′ x , X′O 4-y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is P and X″ is P; and 0<x<3; and 0<y<4.
13 . A battery according to claim 12 , wherein XY 4 is PO 4-x F x , and 0<x≦1.
14 . A battery according to claim 1 , wherein Z comprises F, and 0.1<d≦4.
15 . A battery according to claim 1 , wherein said carbonate comprises an alkylene carbonate having a ring size of from 5 to 8 atoms and is unsubstituted or substituted with lower alkyl on one or more carbon atoms.
16 . A battery according to claim 1 , wherein said carbonate comprises a C 1 -C 6 alkyl carbonate which is unsubstituted or substituted with C 1 -C 4 alkyl on one or more carbon atoms.
17 . A battery according to claim 1 , wherein said cyclic ester has a ring size of from 4 to 7 atoms, and is unsubstituted or substituted on one or more carbon atoms with a lower alkyl group.
18 . A battery according to claim 17 , wherein said carbonate comprises an alkylene carbonate, and the weight ratio of said cyclic ester to said alkylene carbonate is from about 1:1 to about 5:1.
19 . A battery according to claim 18 , wherein said carbonate additionally comprises an alkyl carbonate.
20 . A battery according to claim 18 , wherein said carbonate is ethylene carbonate and said cyclic ester is γ-butyrolactone.
21 . A battery comprising:
(a) a first electrode comprising an active material of the formula Li a M b (PO 4 )Z d , wherein
(i) 0.1<a≦4;
(ii) M is one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 1≦b≦3; and
(iii) Z is halogen, and 0.1<d≦4; and
wherein M, Z, a, b, and d are selected so as to maintain electroneutrality of said compound;
(b) a second electrode which is a counter-electrode to said first electrode; and (c) an electrolyte comprising a mixture of a cyclic ester and a carbonate selected from the group consisting of alkyl carbonates, alkylene carbonates, and mixtures thereof.
22 . A battery according to claim 21 , wherein 0.2≦a≦1.
23 . A battery according to claim 22 , wherein M comprises M′ 1-m M″ m , where M′ is at least one element from Groups 4 to 11 of the Periodic Table; M″ is at least one element from Groups 2, 3, and 12-16 of the Periodic Table; and 0<m<1.
24 . A battery according to claim 23 , wherein M′ is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof, and M″ is selected from the group consisting of Mg, Ca, Zn, Ba, Al, and mixtures thereof.
25 . A battery according to claim 21 , wherein said carbonate comprises an alkylene carbonate having a ring size of from 5 to 8 atoms and is unsubstituted or substituted with lower alkyl on one or more carbon atoms.
26 . A battery according to claim 21 , wherein said carbonate comprises a C 1 -C 6 alkyl carbonate which is unsubstituted or substituted with C 1 -C 4 alkyl on one or more carbon atoms.
27 . A battery according to claim 25 , wherein said cyclic ester has a ring size of from 4 to 7 atoms, and is unsubstituted or substituted on one or more carbon atoms with a lower alkyl group.
28 . A battery according to claim 26 , wherein said alkylene carbonate is ethylene carbonate, said cyclic ester is γ-butyrolactone, and the weight ratio of said cyclic ester to said alkylene carbonate is from about 1:1 to about 5:1.
29 . A battery comprising:
(a) a first electrode comprising an active material of the formula Li a Co e Fe f M 1 g M 2 h M 3 i XY 4 wherein
(i) 0<a≦2, e>0, and f>0;
(ii) M 1 is one or more transition metals, where g≧0;
(iii) M 2 is one or more +2 oxidation state non-transition metals, where h≧0;
(iv) M 3 is one or more +3 oxidation state non-transition metals, where i≧0; and
(v) XY 4 is selected from the group consisting of X′O 4-x Y′ x , X′O 4-y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; X″ is selected from the group consisting of P, As, Sb, Si, Ge, V and mixtures thereof; Y′ is selected from the group consisting of halogen, S, N, and mixtures thereof; 0≦x≦3; and 0<y≦2; and
wherein (e+f+g+h+i)<2, and M 1 , M 2 , M 3 , XY 4 , a, e, f, g, h, i, x, and y are selected so as to maintain electroneutrality of said compound; and (b) a second electrode which is a counter-electrode to said first electrode; and (c) an electrolyte comprising an electrolyte salt, a cyclic ester and a carbonate selected from the group consisting of alkyl carbonates, alkylene carbonates, and mixtures thereof.
30 . A battery according to claim 29 , wherein 0.8≦(e+f+g+h+i)≦1.2.
31 . A battery according to claim 30 , wherein 0.9≦(e+f+g+h+i)≦1.
32 . A battery according to claim 30 , wherein e≧0.5.
33 . A battery according to claim 32 , wherein e≧0.8.
34 . A battery according to claim 31 , wherein 0.01≦f≦0.5.
35 . A battery according to claim 34 , wherein 0.05≦f≦0.15.
36 . A battery according to claim 31 , wherein 0.01≦g≦0.5.
37 . A battery according to claim 36 , wherein 0.05≦g≦0.2.
38 . A battery according to claim 36 , wherein M 1 is selected from the group consisting of Ti, V, Cr, Mn, Ni, Cu and mixtures thereof.
39 . A battery according to claim 38 , wherein M 1 is selected from the group consisting of Mn, Ti, and mixtures thereof.
40 . A battery according to claim 31 , wherein (h+i)>0.
41 . A battery according to claim 40 , wherein 0.01≦(h+i)≦0.5.
42 . A battery according to claim 41 , wherein 0.02≦(h+i)≦0.3.
43 . A battery according to claim 41 , wherein 0.01≦h≦0.2.
44 . A battery according to claim 43 , wherein 0.01≦h≦0.1.
45 . A battery according to claim 43 , wherein M 2 is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.
46 . A battery according to claim 45 , wherein M 2 is Mg.
47 . A battery according to claim 41 , wherein 0.01≦i≦0.2.
48 . A battery according to claim 47 , wherein 0.01≦i≦0.1.
49 . A battery according to claim 47 , wherein M is selected from the group consisting of B, Al, Ga, In and mixtures thereof.
50 . A battery according to claim 49 , wherein M 3 is Al.
51 . A battery according to claim 29 , wherein XY 4 is PO 4 .
52 . A battery according to claim 51 , wherein e≧0.8, and 0.05≦f≦0.15.
53 . A battery according to claim 52 , wherein 0.01≦h≦0.1.
54 . A battery according to claim 53 , wherein M 2 is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.
55 . A battery according to claim 52 , wherein 0.01≦i≦0.1.
56 . A battery according to claim 55 , wherein M 3 is Al.
57 . A battery according to claim 29 , wherein XY 4 is PO 4-x F x , and 0<x≦1.
58 . A battery according to claim 57 , wherein 0.01≦x≦0.05.
59 . A battery according to claim 57 , wherein e≧0.8, and 0.05≦f≦0.15.
60 . A battery according to claim 59 , wherein 0.01≦h≦0.1.
61 . A battery according to claim 60 , wherein M 2 is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.
62 . A battery according to claim 59 , wherein 0.01≦i≦0.1.
63 . A battery according to claim 62 , wherein M 3 is Al.
64 . A battery according to claim 29 , wherein said carbonate comprises an alkylene carbonate having a ring size of from 5 to 8 atoms and is unsubstituted or substituted with lower alkyl on one or more carbon atoms.
65 . A battery according to claim 64 , wherein said alkylene carbonate is selected from the group consisting of ethylene carbonate, 1,3-propylene carbonate, 1,4-butylene carbonate, 1,5-pentylene carbonate, 1,2-propylene carbonate, 2,3-butylene carbonate, 1,2-butylene carbonate, and mixtures thereof.
66 . A battery according to claim 65 , wherein said alkylene carbonate is ethylene carbonate.
67 . A battery according to claim 29 , wherein said carbonate comprises a C 1 -C 6 alkyl carbonate which is unsubstituted or substituted with C 1 -C 4 alkyl on one or more carbon atoms.
68 . A battery according to claim 67 , wherein said alkyl carbonate is selected from the group consisting of diethyl carbonate, ethyl methyl carbonate, dimethyl carbonate, and mixtures thereof.
69 . A battery according to claim 66 , wherein said cyclic ester has a ring size of from 4 to 7 atoms, and is unsubstituted or substituted on one or more carbon atoms with a lower alkyl group.
70 . A battery according to claim 69 , wherein said cyclic ester is selected from the group consisting of substituted or unsubstituted β-propiolactone; substituted or unsubstituted γ-butyrolactone, substituted or unsubstituted δ-valerolactone, substituted or unsubstituted ε-caprolactone, and mixtures thereof.
71 . A battery according to claim 69 , wherein said cyclic ester is γ-butyrolactone.
72 . A battery according to claim 29 , wherein said electrolyte salt is a lithium salt selected from the group consisting of LiAsF 6 , LiPF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiAlCl 4 , LiBr, LiBF 4 , LiSO 3 CF 3 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , and mixtures thereof.
73 . A battery according to claim 72 , wherein said salt is LiBF 4 .
74 . A battery according to claim 29 , wherein said cyclic ester comprises at least about 60% of said electrolyte, and the weight ratio of said cyclic ester to said alkylene carbonate is from about 1:1 to about 5:1.
75 . A battery according to claim 74 , wherein said weight ratio is about 3:1.
76 . A lithium battery of claim 29 , wherein said first electrode is a cathode, and said second electrode is an insertion anode.
77 . A lithium battery of claim 76 , wherein said second electrode comprises a material selected from the group consisting of metal oxides, metal chalcogenides, carbon, graphite, and mixtures thereof.
78 . A battery comprising:
(a) a first electrode comprising an active material having an olivine structure, of the formula LiM(PO 4-x Y′ x ) wherein M is M 1 g M 2 h M 3 i M 4 j , and
(i) M 1 is one or more transition metals;
(ii) M 2 is one or more +2 oxidation state non-transition metals;
(iii) M 3 is one or more +3 oxidation state non-transition metals,
(iv) M 4 is one or more +1 oxidation state non-transition metals;
(v) Y′ is halogen; and
g>0, each of h, i, and j≧0; (g+h+i+j)≦1, and 0≦x≦0.5; and (b) a second electrode which is a counter-electrode to said first electrode; and (c) an electrolyte comprising an electrolyte salt, an alkylene carbonate, and a cyclic ester and a carbonate selected from the group consisting of alkyl carbonates, alkylene carbonates, and mixtures thereof.
79 . An electrode active material according to claim 78 , wherein g≧0.8.
80 . An electrode active material according to claim 79 , wherein g≧0.9.
81 . An electrode active material according to claim 79 , wherein M 1 is a +2 oxidation state transition metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, and mixtures thereof.
82 . An electrode active material according to claim 81 , wherein M 1 is selected from the group consisting of Fe, Co, and mixtures thereof.
83 . An electrode active material according to claim 79 , wherein (h+i)>0.
84 . An electrode active material according to claim 83 , wherein 0.01≦(h+i)≦0.5.
85 . An electrode active material according to claim 84 , wherein 0.02≦(h+i)≦0.3.
86 . An electrode active material according to claim 83 , wherein 0.01≦h≦0.2.
87 . An electrode active material according to claim 86 , wherein 0.01≦h≦0.1.
88 . An electrode active material according to claim 86 , wherein M 2 is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.
89 . An electrode active material according to claim 83 , wherein 0.01≦i≦0.2.
90 . An electrode active material according to claim 89 , wherein 0.01≦i≦0.1.
91 . An electrode active material according to claim 89 , wherein M 3 is Al.
92 . An electrode active material according to claim 79 , wherein j=0.
93 . An electrode active material according to claim 79 , wherein 0.01≦j≦0.1.
94 . An electrode active material according to claim 93 , wherein M 4 is selected from the group consisting of Li, Na, and K.
95 . An electrode active material according to claim 94 , wherein M 4 is Li.
96 . An electrode active material according to claim 79 , wherein x=0.
97 . An electrode active material according to claim 96 , wherein g≧0.8, and (g+h+i+j)=1.
98 . An electrode active material according to claim 97 , wherein 0.01≦h≦0.1 and M 2 is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.
99 . An electrode active material according to claim 97 , wherein 0.01≦i≦0.1, and M 3 is Al.
100 . An electrode active material according to claim 97 , wherein 0.01≦j≦0.1, and M 4 is Li.
101 . An electrode active material according to claim 78 , wherein 0<x≦1.
102 . An electrode active material according to claim 101 , wherein 0.01≦x≦0.05, and (g+h+i+j)<1.
103 . An electrode active material according to claim 102 , wherein g≧0.8.
104 . An electrode active material according to claim 103 , wherein 0.01≦h≦0.1, and M 2 is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.
105 . An electrode active material according to claim 103 , wherein 0.01≦i≦0.1, and M 3 is Al.
106 . An electrode active material according to claim 103 , wherein j=0.
107 . An electrode active material according to claim 106 , wherein (g+h+i)=1-x.
108 . A battery according to claim 81 , wherein said active material is selected from the group consisting of: LiFePO 4 ; LiFe 0.9 Mg 0.1 PO 4 ; LiFe 0.8 Mg 0.2 PO 4 ; Li 1.025 Cu 0.85 Fe 0.05 Al 0.025 Mg 0.05 PO 4 , Li 1.025 Co 0.80 Fe 0.10 Al 0.025 Mg 0.05 PO 4 , Li 1.025 Co 0.75 Fe 0.05 Al 0.025 Mg 0.05 PO 4 , Li 1.025 Co 0.7 (Fe 0.4 Mn 0.6 ) 0.2 Al 0.025 Mg 0.05 PO 4 , LiCo 0.8 Fe 0.1 Al 0.025 Ca 0.05 PO 3.975 F 0.025 , LiCo 0.8 Fe 0.1 Al 0.025 Mg 0.05 PO 3.975 F 0.025 , LiCo 0.8 Fe 0.1 Ti 0.025 Mg 0.05 PO 4 ; Li 1.025 Co 0.8 Fe 0.1 Ti 0.025 Al 0.025 PO 4 ; Li 1.025 Co 0.8 Fe 0.1 Ti 0.025 Mg 0.025 PO 3.975 F 0.025 ; LiCu 0.825 Fe 0.1 Ti 0.025 Mg 0.025 PO 4 ; LiCu 0.85 Fe 0.075 Ti 0.025 Mg 0.025 PO 4 ; and mixtures thereof.
109 . A battery according to claim 29 , wherein said active material is LiCo 0.8 Fe 0.1 Al 0.025 Mg 0.05 PO 3.975 F 0.025 .
110 . A battery according to claim 80 , wherein said carbonate comprises an alkylene carbonate having a ring size of from 5 to 8 atoms and is unsubstituted or substituted with lower alkyl on one or more carbon atoms.
111 . A battery according to claim 110 , wherein said alkylene carbonate is ethylene carbonate.
112 . A battery according to claim 80 , wherein said carbonate comprises C 1 -C 6 alkyl carbonate which is unsubstituted or substituted with C 1 -C 4 alkyl on one or more carbon atoms.
113 . A battery according to claim 112 , wherein said alkyl carbonate is diethyl carbonate.
114 . A battery according to claim 80 , wherein said cyclic ester has a ring size of from 4 to 7 atoms, and is unsubstituted or substituted on one or more carbon atoms with a lower alkyl group.
115 . A battery according to claim 114 , wherein said cyclic ester is γ-butyrolactone.
116 . A battery according to claim 80 , wherein said salt is selected from the group consisting of LiAsF 6 , LiPF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiAlCl 4 , LiBr, LiBF 4 , LiSO 3 CF 3 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , and mixtures thereof.
117 . A battery according to claim 80 , wherein the weight ratio of said cyclic ester to said alkylene carbonate is from about 1:1 to about 5:1.
118 . A battery according to claim 117 , wherein said weight ratio is about 3:1.
119 . A lithium battery of claim 80 , wherein said first electrode is a cathode, and said second electrode is an insertion anode.
120 . A lithium battery of claim 119 , wherein said second electrode comprises a material selected from the group consisting of metal oxides, metal chalcogenides, carbon, graphite, and mixtures thereof.
121 . A battery comprising:
(a) a first electrode comprising an active material of the formula LiCo 0.8 Fe 0.1 Al 0.025 Mg 0.05 PO 3.975 F 0.025 (b) a second electrode which is a counter-electrode to said first electrode; and (c) an electrolyte comprising
(i) an electrolyte salt;
(ii) an alkylene carbonate having a ring size of from 5 to 8 atoms and unsubstituted or substituted with lower alkyl on one or more carbon atoms; and
(iii) a cyclic ester having a ring size of from 4 to 7 atoms, and is unsubstituted or substituted on one or more carbon atoms with a lower alkyl group.
122 . A battery according to claim 120 , wherein said first electrode is a cathode, said second electrode is an insertion anode, said alkylene ester is ethylene carbonate; said cyclic ester is γ-butyrolactone; the weight ratio of said cyclic ester to said alkylene carbonate is from about 1:1 to about 5:1; and said electrolyte salt is LiBF 4 .Cited by (0)
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