Chemically stable solid lithium ion conductor
The present invention concerns chemically stable solid lithium ion conductors, processes for their production and their use in batteries, accumulators, supercaps and electrochromic devices.
1. A solid ion conductor, characterized in that it has a garnet-like crystal structure and that it has a stoichiometric composition L 5+x AyG z M 2 O 12 , wherein
L is in each case independently an arbitrary preferably monovalent cation,
A is in each case independently a monovalent, divalent, trivalent or tetravalent cation,
G is in each case independently a monovalent, divalent, trivalent or tetravalent cation
M is in each case independently a trivalent, tetravalent or pentavalent cation,
0<x≦2, 0≦y≦3, 0≦z≦3 and
wherein O can be partially or completely replaced by divalent and/or trivalent anions such as e.g. N 3− , and wherein at least one of A and G is a divalent cation.
2. Solid ion conductor as claimed in claim 1 , wherein L is selected from Li, Na and K can in each case be the same or different.
3. Solid ion conductor as claimed in claim 2 , wherein L is Li.
4. A solid ion conductor, characterized in that it has a garnet-like crystal structure and that it has a stoichiometric composition L 5+x AyG z M 2 O 12 , wherein
L is in each case independently an arbitrary preferably monovalent cation,
A is in each case independently a monovalent, divalent, trivalent or tetravalent cation,
G is in each case independently a monovalent, divalent, trivalent or tetravalent cation
M is in each case independently a trivalent, tetravalent or pentavalent cation,
0<x≦2, 0≦y≦3, 0≦z≦3 and wherein O can be partially or completely replaced by divalent and/or trivalent anions such as e.g. N 3− , wherein A is selected from divalent cations preferably alkaline earth metal ions.
5. Solid ion conductor as claimed in claim 1 , wherein M is selected from transition metal ions.
6. The solid ion conductor of claim 4 , wherein A is selected from Ca, Sr and/or Ba and wherein M is selected from Nb and Ta.
7. The solid ion conductor of claim 4 , wherein A is selected from Sr and Ba and wherein M is Ta.
8. Solid ion conductor as claimed in claim 1 , characterized in that it is stable towards elemental lithium at lithium activities corresponding to a voltage of 5 V.
9. A solid ion conductor that has a garnet-like crystal structure and a stoichiometric composition L 5+x AyG z M 2 O 12 , wherein
L is in each case independently an arbitrary preferably monovalent cation,
A is in each case independently a monovalent, divalent, trivalent or tetravalent cation,
G is in each case independently a monovalent, divalent, trivalent or tetravalent cation
M is in each case independently a trivalent, tetravalent or pentavalent cation,
1≦x≦2, 0≦y≦3, 0≦z≦3 and wherein O can be partially or completely replaced by divalent and/or trivalent anions such as e.g. N 3− .
10. A process for producing a solid ion carrier that has a garnet-like crystal structure and that has a stoichiometric composition L 5+x AYG z M 2 O 12 , wherein
L is in each case independently an arbitrary preferably monovalent cation,
A is in each case independently a monovalent, divalent, trivalent or tetravalent cation,
G is in each case independently a monovalent, divalent, trivalent or tetravalent cation
M is in each case independently a trivalent, tetravalent or pentavalent cation,
0≦x≦2, 0≦y≦3, 0≦z≦3 and wherein O can be partially or completely replaced by divalent and/or trivalent anions such as e.g. N 3− , and wherein at least one of A and G is a divalent cation, comprising the steps of
(a) reacting salts and/or oxides of L, A, G, and M by mixing to form a reaction mixture;
(b) ball-milling, preferably using zirconium oxide balls in 2-propanol;
(c) heating the mixture from (a) in air for 2-10 hours to 400-1000° C.;
(d) ball-milling, preferably using zirconium balls in 2-propanol;
(e) pressing the mixture with isostatic pressure into pellets; and
(f) sintering the pellets covered with a powder of the same composition for 10-50 hours at 700-1200° C.
11. A process for producing a solid ion carrier that has a garnet-like crystal structure and that has a stoichiometric composition L 5+x AYG z M 2 O 12 , wherein
L is in each case independently an arbitrary preferably monovalent cation,
A is in each case independently a monovalent, divalent, trivalent or tetravalent cation,
G is in each case independently a monovalent, divalent, trivalent or tetravalent cation
M is in each case independently a trivalent, tetravalent or pentavalent cation,
0<x≦2, 0≦y≦3, 0≦z≦3 and wherein O can be partially or completely replaced by divalent and/or trivalent anions such as e.g. N 3− , and wherein A is selected from divalent cations preferably alkaline earth metal ions, comprising the steps of
(a) reacting salts and/or oxides of L, A, G, and M by mixing to form a reaction mixture;
(b) ball-milling, preferably using zirconium oxide balls in 2-propanol;
(c) heating the mixture from (a) in air for 2-10 hours to 400-1000° C.;
(d) ball-milling, preferably using zirconium balls in 2-propanol;
(e) pressing the mixture with isostatic pressure into pellets; and
(f) sintering the pellets covered with a powder of the same composition for 10-50 hours at 700-1200° C.