Back to results
US 5,630,994 AGranted
Non-aqueous solution preparation of doped and undoped lixmnyoz
OwnerTimothy J. Boyle, James A. Voigtinventors
Life of this patent
Estimating the term…
Abstract
A method for generation of phase-pure doped and undoped Li.sub.x Mn.sub.y O.sub.z precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder.
Claims21
A method comprising preparing phase-pure LiMn.sub.2 O.sub.4 comprising the steps of:
- (a) preparing an approximately 3.4M solution of Mn(NO.sub.3).sub.2 .multidot.xH.sub.2 O in tetrahydrofuran (THF) and stirring the solution thereby substituting the H.sub.2 O with THF to form Mn(NO.sub.3).sub.2 .multidot.xTHF;
- (b) removing all the unreacted THF solvent in vacuo leaving substantially pure Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 ;
- (c) mixing an approximately 0.87M solution of LiNO.sub.3 in an organic solvent with an approximately 0.40M solution of the Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 in said organic solvent, in the volume ratio of about 1.0:4.4, respectively;
- (d) mixing an approximately 6.0M solution of Me.sub.4 NOH.multidot.6H.sub.2 O in said organic solvent with an approximately 8.3M solution of H.sub.2 C.sub.2 O.sub.4 in said organic solvent, in the volume ratio of about 1.0:0.36 respectively, while stirring under an inert gas and then removing the solvent in vacuo to form (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 powder;
- (e) mixing an approximately 0.29M solution of said (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 in said organic solvent with the mixed LiNO.sub.3 /Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 organic-solvent solutions in the volume ratio of about 1.0 part of the (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 solution to about 0.26 part of the mixed LiNO.sub.3 /Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 solutions, respectively, to form a precipitate;
- (f) separating the precipitate from solution and processing the precipitate by drying and heating to facilitate crystallization of LiMn.sub.2 O.sub.4.
3 more elements
A method comprising preparing phase-pure Li.sub.2 Mn.sub.2 O.sub.4 comprising the steps of:
- (a) preparing an approximately 3.4M solution of/Mn(NO.sub.3).sub.2 .multidot.xH.sub.2 O in tetrahydrofuran (THF) and stirring the solution thereby substituting the H.sub.2 O with THF to form Mn(NO.sub.3).sub.2 .multidot.xTHF;
- (b) removing all the unreacted THF solvent in vacuo leaving substantially pure Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 ;
- (c) mixing an approximately 1.7M solution of LiNO.sub.3 in an organic solvent with an approximately 0.40M solution of the Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 in said organic solvent, in the volume ratio of about 1.0:4.4, respectively;
- (d) mixing an approximately 6.0M solution of Me.sub.4 NOH.multidot..sub.6 H.sub.2 O in said organic solvent with an approximately 8.3M solution of H.sub.2 C.sub.2 O.sub.4 in said organic solvent, in the volume ratio of about 1.0:0.36 respectively, while stirring under an inert gas and then removing the solvent in vacuo to form (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 powder;
- (e) mixing an approximately 0.29M solution of said (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 in said organic solvent with the mixed LiNO.sub.3 /Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 organic-solvent solutions in the volume ratio of about 1.0 part of the (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 solution to about 0.26 part of the mixed LiNO.sub.3 /Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 solution, respectively, to form a precipitate;
- (f) separating the precipitate from solution and processing the precipitate by drying and heating to facilitate crystallization of Li.sub.2 Mn.sub.2 O.sub.4.
3 more elements
A method comprising preparing phase-pure Li.sub.3 Mn.sub.2 O.sub.4, comprising the steps of:
- (a) preparing an approximately 3.4M solution of Mn(NO.sub.3).sub.2 .multidot.xH.sub.2 O in tetrahydrofuran (THF) and stirring the solution thereby substituting the H.sub.2 O with THF to form Mn(NO.sub.3).sub.2 .multidot.xTHF;
- (b) removing all the unreacted THF solvent in vacuo leaving substantially pure Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 ;
- (c) mixing an approximately 2.6M solution of LiNO.sub.3 in an organic solvent with an approximately 0.40M solution of the Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 in said organic solvent, in the volume ratio of about 1.0:4.4, respectively;
- (d) mixing an approximately 6.0M solution of Me.sub.4 NOH.multidot.6H.sub.2 O in said organic solvent with an approximately 8.3M solution of H.sub.2 C.sub.2 O.sub.4 in said organic solvent, in the volume ratio of about 1.0:0.36 respectively, while stirring under an inert gas and then removing the solvent in vacuo to form (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 powder;
- (e) mixing an approximately 0.29M solution of said (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 in said organic solvent with the mixed LiNO.sub.3 /Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 organic-solvent solutions in the volume ratio of about 1.0 part of the (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 solution to about 0.26 part of the mixed LiNO.sub.3 /Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 solution, respectively, to form a precipitate;
- (f) separating the precipitate from solution and processing the precipitate by drying and heating to facilitate crystallization of Li.sub.3 Mn.sub.2 O.sub.4.
3 more elements
A method comprising preparing phase-pure DLi.sub.8 Mn.sub.15 O.sub.32, where D is selected from the group consisting of Al.sup.+3, Co.sup.+2, Ni.sup.+2, and combinations thereof, comprising the steps of:
- (a) preparing an approximately 3.4M solution of Mn(NO.sub.3).sub.2 .multidot.xH.sub.2 O in tetrahydrofuran (THF) and stirring the solution for about 12 h thereby substituting the H.sub.2 O with THF to form Mn(NO.sub.3).sub.2 .multidot.xTHF;
- (b) removing all the unreacted THF solvent in vacuo leaving substantially pure Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 ;
- (c) mixing an approximately 0.17M solution of D(NO.sub.3).sub.n .multidot.3nH.sub.2 O, where n is 2 or 3, in an organic solvent with an approximately 1.3M solution of the Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 in said organic solvent, in the volume ratio of about 1.0:4.4, respectively, and adding approximately 0.054 mole of LiNO.sub.3 to the stirring solutions;
- (d) mixing an approximately 6.0M solution of Me.sub.4 NOH.multidot.6H.sub.2 O in said organic solvent with an approximately 8.3M solution of H.sub.2 C.sub.2 O.sub.4 in said organic solvent, in the volume ratio of about 1.0:0.36 respectively, while stirring under an inert gas and then removing the solvent in vacuo to form (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 powder;
- (e) mixing an approximately 1.9M solution of said (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 in said organic solvent with the mixed D(NO.sub.3).sub.n .multidot.3nH.sub.2 O/Mn(NO.sub.3).sub.2 .multidot.TH.sub.0.98 organic-solvent solutions in the volume ratio of about 1.0 part of the (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 solution to about 0.26 part of the mixed D(NO.sub.3).sub.n .multidot.3nH.sub.2 O/MnCNO.sub.3).sub.2 .multidot.THF.sub.0.98 solutions, respectively, to form a precipitate;
- (f) separating the precipitate from solution and processing the precipitate by drying and heating to facilitate crystallization of DLi.sub.8 Mn.sub.15 O.sub.32.
3 more elements
A method comprising preparing phase-pure D.sub.2 Li.sub.8 Mn.sub.15 O.sub.32, where D is selected from the group consisting of Al.sup.+3, Co.sup.+2, Ni.sup.+2, and combinations thereof, comprising the steps of:
- (a) preparing an approximately 3.4M solution of Mn(NO.sub.3).sub.2 .multidot.xH.sub.2 O in tetrahydrofuran (THF) and stirring the solution for about 12 h thereby substituting the H.sub.2 O with THF to form Mn(NO.sub.3).sub.2 .multidot.THF;
- (b) removing all the unreacted THF solvent in vacuo leaving substantially pure Mn(NO.sub.3).sub.2 .multidot.xTHF;
- (c) mixing an approximately 0.36M solution of D(NO.sub.3).sub.n .multidot.3nH.sub.2 O, where n is 2 or 3, in an organic solvent with an approximately 1.3M solution of the Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 in said organic solvent, in the volume ratio of about 1.0:4.4, respectively, and adding approximately 0.054 mole of LiNO.sub.3 to the stirring solutions;
- (d) mixing an approximately 6.0M solution of Me.sub.4 NOH.multidot.6H.sub.2 O in said organic solvent with an approximately 8.3M solution of H.sub.2 C.sub.2 O.sub.4 in said organic solvent, in the volume ratio of about 1.0:0.36 respectively, while stirring under an inert gas and then removing the solvent in vacuo to form (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 powder;
- (e) mixing an approximately 1.9M solution of said (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 in said organic solvent with the mixed D(NO.sub.3).sub.n .multidot.3H.sub.2 O/Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 organic-solvent solutions in the volume ratio of about 1.0 part of the (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 solution to about 0.26 part of the mixed D(NO.sub.3).sub.n 3n.multidot.H.sub.2 O/Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 solutions, respectively, to form a precipitate;
- (f) separating the precipitate from solution and processing the precipitate by drying and heating to facilitate crystallization of D.sub.2 Li.sub.8 Mn.sub.15 O.sub.32.
3 more elements
A method comprising preparing phase-pure D.sub.3 Li.sub.8 Mn.sub.15 O.sub.32, where D is selected from the group consisting of Al.sup.+3, Co.sup.+2, Ni.sup.+2, and combinations thereof, comprising the steps of:
- (a) preparing an approximately 3.4M solution of Mn(NO.sub.3).sub.2 .multidot.xH.sub.2 O in tetrahydrofuran (THF) and stirring the solution for about 12 h thereby substituting the H.sub.2 O with THF to form Mn(NO.sub.3).sub.2 .multidot.xTHF;
- (b) removing all the unreacted THF solvent in vacuo leaving substantially pure Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 ;
- (c) mixing an approximately 0.54M solution of D(NO.sub.3).sub.n .multidot.3nH.sub.2 O, where n is 2 or 3, in an organic solvent with an approximately 1.3M solution of the Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 in said organic solvent, in the volume ratio of about 1.0:4.4, respectively, and adding approximately 0.054 mole of LiNO.sub.3 to the stirring solutions;
- (d) mixing an approximately 6.0M solution of Me.sub.4 NOH.multidot.6H.sub.2 O in said organic solvent with an approximately 8.3M solution H.sub.2 C.sub.2 O.sub.4 in said organic solvent, in the volume 12 ratio of about 1.0:0.36 respectively, while stirring under an inert gas and then removing the solvent in vacuo to form (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 powder;
- (e) mixing an approximately 1.9M solution of said (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 in said organic solvent with the mixed D(NO.sub.3).sub.n .multidot.3nH.sub.2 O/Mn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 organic-solvent solutions in the volume ratio of about 1.0 part of the (Me.sub.4 N).sub.2 C.sub.2 O.sub.4 solution to about 0.26 part of the mixed D(NO.sub.3).sub.n.multidot. 3nH.sub.2 OMn(NO.sub.3).sub.2 .multidot.THF.sub.0.98 solutions, respectively, to form a precipitate;
- (f) separating the precipitate from solution and processing the precipitate by drying and heating to facilitate crystallization of D.sub.3 Li.sub.8 Mn.sub.15 O.sub.32.
3 more elements
Dependencies are inferred from the claim text.