Amorphous cationic conductors

Claim 2

An amorphous cationic conductor of lithium comprising a composition corresponding to the general formula: {B.sub.2 O.sub.3, xM, yN}, aLi.sub.2 O, bLi.sub.z Q in which: M is chosen from the group formed by: Al.sub.2 O.sub.3, V.sub.2 O.sub.5, P.sub.2 O.sub.5, As.sub.2 O.sub.5 and As.sub.2 O.sub.3 ; N is chosen from the group formed by: SiO.sub.2 and GeO.sub.2 ; Q is chosen from the group consisting of: F - , Cl - , Br - , S 2- , SO 4 2- , MoO 4 2- , N 3- , PO 4 3- and WO 4 2- ; 0≦x≦0.35 0≦y≦0.8 0<a≦2 0<b<1.5 b≦2a; and z=1 or 2 or 3 according to whether Q is mono-, bi- or tri-valent.

Claim 3

A conductor according to claim 1, wherein in the said formula: x=y=0; 0<a≦0.85; and if z=1, Q is chosen from F - , Cl - or Br - and b≦0.85; or if z=2, Q is chosen from S 2- or SO 4 2- and b≦0.3; or if z=3, Q is chosen from N 3- or PO 4 3- and b≦0.2.

Claim 4

A conductor according to claim 1, having one of the following formulae: B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.57LiCl B.sub.2 O.sub.3, 0.85Li.sub.2 O, 0.29LiCl B.sub.2 O.sub.3, 0.43Li.sub.2 O, 0.29LiCl B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.21LiCl B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.21LiBr B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.29Li.sub.2 S B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.29Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Li.sub.3 PO.sub.4 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Li.sub.3 N.

Claim 5

A conductor according to claim 1, wherein in the said formula, y=0, 0<x≦0.30, 0<a≦0.85; and if z=1, Q is chosen from F - ; Cl - , or Br - and b≦1; or if z=2, Q is SO 4 2- and b≦0.3; or if z=3, Q is PO 4 3- and b≦0.2.

Claim 6

A conductor according to claim 1, having one of the following formulae: B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.28Al.sub.2 O.sub.3, LiCl B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Al.sub.2 O.sub.3, 0.28Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14P.sub.2 O.sub.5, 0.21LiBr B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.21LiBr, 0.14Al.sub.2 O.sub.3 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Li.sub.3 PO.sub.4, 0.14Al.sub.2 O.sub.3 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Al.sub.2 O.sub.3, 0.57LiF B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Al.sub.2 O.sub.3, 0.70LiCl.

Claim 7

A conductor according to claim 1, wherein, in the formula: x=0, 0<y≦0.7 0<a≦1.7 if z=1, Q is chosen from F - , Cl - or Br - and b≦1; or if z=2, Q is SO 4 2- and b≦1.2.

Claim 8

A conductor according to claim 1, having one of the following formulae: B.sub.2 O.sub.3, 0.57SiO.sub.2, 1.70Li.sub.2 O, Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.43Si.sub.2 O, Li.sub.2 O, 1.14Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.57SiO.sub.2, 1.5Li.sub.2 O, Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.43SiO.sub.2, 1.43Li.sub.2 O, 1.14Li.sub.2 SO.sub.4.

Claim 9

A method of preparing an amorphous cationic conductor, of claim 1 wherein (A) the starting products--boric anhydride, lithium oxide or a compound giving rise to Li 2 O and lithium salt or (B) said starting products and at least one of the M and N compounds--are melted for about five minutes at a temperature lying between 700° and 1200° C., then they are hardened and annealed at a temperature about 50° C. lower than the recrystallization temperature of the cationic conductor, for about 15 hours.

Claim 10

The process of claim 8 wherein the compound giving rise to Li 2 O is Li 2 CO 3 or LiOH.

Claim 11

A process for forming of electrodes specific to lithium which comprises forming the electrodes of a composition corresponding to the general formula: {B.sub.2 O.sub.3, xM, yN}, aLi.sub.2 O, bLi.sub.z Q in which: M is chosen from the group formed by: Al.sub.2 O.sub.3, V.sub.2 O.sub.5, P.sub.2 O.sub.5, As.sub.2 O.sub.5 and As.sub.2 O.sub.3 ; N is chosen from the group formed by: SiO.sub.2 and GeO.sub.2 ; Q is chosen from the group consisting of: F - , Cl - , Br - , S 2- , SO 4 2- , MoO 4 2- , PO 4 3- , and WO 4 2- ; 0≦x≦0.35 0≦y≦0.8 0<a≦2 0<b<1.5 b≦2a; and z=1 or 2 or 3 according to whether Q is mono-, bi- or tri-valent.

Claim 12

A process for forming of electrodes specific to lithium which comprises forming the electrodes of a composition corresponding to the general formula: {B.sub.2 O.sub.3, xM, yN}, aLi.sub.2 O, bLi.sub.z Q in which: M is chosen from the group formed by: Al.sub.2 O.sub.3, V.sub.2 O.sub.5, P.sub.2 O.sub.5, As.sub.2 O.sub.5 and As.sub.2 O.sub.3 ; N is chosen from the group formed by: SiO.sub.2 and GeO.sub.2 ; Q is chosen from the group consisting of: F - , Cl - , Br - , S 2- , SO 4 2- , MoO 4 2- , PO 4 3- , and WO 4 2- ; 0≦x≦0.35 0≦y≦0.8 0<a≦2 0<b<1.5 b≦2a; and z=1 or 2 or 3 according to whether Q is mono-, bi- or tri-valent.

Claim 13

A process for forming selective membranes for producing an purifying solutions which contain lithium ions which comprises forming the membranes of a composition corresponding to the general formula: {B.sub.2 O.sub.3, xM, yN}, aLi.sub.2 O, bLi.sub.z Q in which: M is chosen from the group formed by: Al.sub.2 O.sub.3, V.sub.2 O.sub.5, P.sub.2 O.sub.5, As.sub.2 O.sub.5 and As.sub.2 O.sub.3 ; N is chosen from the group formed by: SiO.sub.2 and GeO.sub.2 ; Q is chosen from the group consisting of: F - , Cl - , Br - , S 2- , SO 4 2- , MoO 4 2- , N 3- , PO 4 3- and WO 4 2- ; 0≦x≦0.35 0≦y≦0.8 0<a≦2 0<b<1.5 b≦2a; and z=1 or 2 or 3 according to whether Q is mono-, bi- or tri-valent.

Claim 14

A process for forming selective membranes for producing an purifying solutions which contain lithium ions which comprises forming the membranes of a composition corresponding to the general formula: {B.sub.2 O.sub.3, xM, yN}, aLi.sub.2 O, bLi.sub.z Q in which: M is chosen from the group formed by: Al.sub.2 O.sub.3, V.sub.2 O.sub.5, P.sub.2 O.sub.5, As.sub.2 O.sub.5 and As.sub.2 O.sub.3 ; N is chosen from the group formed by: SiO.sub.2 and GeO.sub.2 ; Q is chosen from the group consisting of: F - , Cl - , Br - , S 2- , SO 4 2- , MoO 4 2- , N 3- , PO 4 3- and WO 4 2- ; 0≦x≦0.35 0≦y≦0.8 0<a≦2 0<b<1.5 b≦2a; and z=1 or 2 or 3 according to whether Q is mono-, bi- or tri-valent.

Claim 15

A process for forming solid electrolytes for electric cells which comprises forming the solid electrolytes of a composition corresponding to the general formula: {B.sub.2 O.sub.3, xM, yN}, aLi.sub.2 O, bLi.sub.z Q in which: M is chosen from the group formed by: Al.sub.2 O.sub.3, V.sub.2 O.sub.5, P.sub.2 O.sub.5, As.sub.2 O.sub.5 and As.sub.2 O.sub.3 ; N is chosen from the group formed by: SiO.sub.2 and GeO.sub.2 ; Q is chosen from the group consisting of: F - , Cl - , Br - , S 2- , SO 4 2- , MoO 2 2- , N 3- , PO 4 3- , and WO 4 2- 0≦x≦0.35 0≦y≦0.8 0<a≦2 0<b<1.5 b≦2a; and z=1 or 2 or 3 according to whether Q is mono-, bi- or tri-valent.

Claim 16

A process for forming solid electrolytes for electric cells which comprises forming the solid electrolytes of a composition corresponding to the general formula: {B.sub.2 O.sub.3, xM, yN}, aLi.sub.2 O, bLi.sub.z Q in which: M is chosen from the group formed by: Al.sub.2 O.sub.3, V.sub.2 O.sub.5, P.sub.2 O.sub.5, As.sub.2 O.sub.5 and As.sub.2 O.sub.3 ; N is chosen from the group formed by: SiO.sub.2 and GeO.sub.2 ; Q is chosen from the group consisting of: F - , Cl - , Br - , S 2- , SO 4 2- , MoO 2 2- , N 3- , PO 4 3- , and WO 4 2- 0≦x≦0.35 0≦y≦0.8 0<a≦2 0<b<1.5 b≦2a; and z=1 or 2 or 3 according to whether Q is mono-, bi- or tri-valent.

Claim 17

The process of claim 12 wherein the composition has one of the following formula: B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.57LiCl B.sub.2 O.sub.3, 0.85Li.sub.2 O, 0.29LiCl B.sub.2 O.sub.3, 0.43Li.sub.2 O, 0.29LiCl B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.21LiCl B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.21LiBr B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.29Li.sub.2 S B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.29Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Li.sub.3 PO.sub.4 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Li.sub.3 N B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.28Al.sub.2 O.sub.3, LiCl B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Al.sub.2 O.sub.3, 0.28Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14P.sub.2 O.sub.5, 0.21LiBr B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.21LiBr, 0.14Al.sub.2 O.sub.3 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Li.sub.3 PO.sub.4, 0.14Al.sub.2 O.sub.3 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Al.sub.2 O.sub.3, 0.57LiF B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Al.sub.2 O.sub.3, 0.70LiCl B.sub.2 O.sub.3, 0.57SiO.sub.2, 1.70Li.sub.2 O, Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.43Si.sub.2 O, Li.sub.2 O, 1.14Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.57SiO.sub.2, 1.5Li.sub.2 O, Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.43SiO.sub.2, 1.43Li.sub.2 O, 1.14Li.sub.2 SO.sub.4.

Claim 18

Electric cells which include an anode based on lithium, a cathode mode of a material with a host structure for lithium and an amorphous cationic conductor of lithium comprising a composition corresponding to the general formula: {B.sub.2 O.sub.3, xM, yN}, aLi.sub.2 O, bLi.sub.z Q in which: M is chosen from the group formed by: Al.sub.2 O.sub.3, V.sub.2 O.sub.5, P.sub.2 O.sub.5, As.sub.2 O.sub.5 and As.sub.2 O.sub.3 ; N is chosen from the group formed by: SiO.sub.2 and GeO.sub.2 ; Q is chosen from the group consisting of; F - , Cl - , Br - , S 2- , SO 4 2- , MoO 4 2- , N 3- , PO 4 3- and WO 4 2- 0≦x≦0.35 0≦y≦0.8 0<a≦2 0<b<1.5 b≦2a; and z=1 or 2 or 3 according to whether Q is mono-, bi- or tri-valent.

Claim 19

Electric cells which include an anode based on lithium, a cathode mode of a material with a host structure for lithium and an amorphous cationic conductor of lithium comprising a composition corresponding to the general formula: {B.sub.2 O.sub.3, xM, yN}, aLi.sub.2 O, bLi.sub.z Q in which: M is chosen from the group formed by: Al.sub.2 O.sub.3, V.sub.2 O.sub.5, P.sub.2 O.sub.5, As.sub.2 O.sub.5 and As.sub.2 O.sub.3 ; N is chosen from the group formed by: SiO.sub.2 and GeO.sub.2 ; Q is chosen from the group consisting of; F - , Cl - , Br - , S 2- , SO 4 2- , MoO 4 2- , N 3- , PO 4 3- and WO 4 2- 0≦x≦0.35 0≦y≦0.8 0<a≦2 0<b<1.5 b≦2a; and z=1 or 2 or 3 according to whether Q is mono-, bi- or tri-valent.

Claim 20

Electric cells according to claim 14, in which the cathode is made of titanium sulphide.

Claim 21

The electric cells of claim 14 wherein the amorphous cationic conductor has one of the following formula: B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.57LiCl B.sub.2 O.sub.3, 0.85Li.sub.2 O, 0.29LiCl B.sub.2 O.sub.3, 0.43Li.sub.2 O, 0.29LiCl B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.21LiCl B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.21LiBr B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.29Li.sub.2 S B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.29Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Li.sub.3 PO.sub.4 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Li.sub.3 N B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.28Al.sub.2 O.sub.3, LiCl B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Al.sub.2 O.sub.3, 0.28Li.sub.2 SO.sub.4 B 2 O 3 , 0.57Li 2 O, 0.14P 2 O 5 , 0.21LiBr B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.2LiBr, 0.14Al.sub.2 O.sub.3 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Li.sub.3 PO.sub.4, 0.14Al.sub.2 O.sub.3 B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Al.sub.2 O.sub.3, 0.57LiF B.sub.2 O.sub.3, 0.57Li.sub.2 O, 0.14Al.sub.2 O.sub.3, 0.70LiCl B.sub.2 O.sub.3, 0.57SiO.sub.2, 1.70Li.sub.2 O, Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.43Si.sub.2 O, Li.sub.2 O, 1.14Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.57SiO.sub.2, 1.5Li.sub.2 O, Li.sub.2 SO.sub.4 B.sub.2 O.sub.3, 0.43SiO.sub.2, 1.43Li.sub.2 O, 1.14Li.sub.2 SO.sub.4.