Process for producing lithium iron phosphate particles and method for producing secondary cell
View Patent ↗The present invention relates to a process for producing lithium iron phosphate particles, wherein the process has a step of obtaining a melt containing, as represented by mol % based on oxides, from 1 to 50% of Li 2 O, from 20 to 50% of Fe 2 O 3 and from 30 to 60% of P 2 O 5 ; a step of cooling and solidifying the melt; a step of pulverizing the solidified product into a desired particle shape; and a step of heating the pulverized product in the air or under oxidizing conditions (0.21<oxygen partial pressure<1.0) at from 350 to 800° C. to precipitate crystals of Li n Fe 2 (PO 4 ) 3 (0<n<3), in this order.
1. A process for producing lithium iron phosphate particles, which comprises:
obtaining a melt containing, as represented by mol % based on oxides, from 1 to 50% of Li 2 O, from 20 to 50% of Fe 2 O 3 and from 30 to 60% of P 2 O 5 ;
cooling and solidifying the melt to obtain a solidified product;
pulverizing the solidified product to obtain a pulverized product; and
heating the pulverized product in the air or under oxidizing conditions with an oxygen partial pressure of higher than 0.21 and at most 1.0 atmosphere from 350 to 800° C. to precipitate crystals of Li n Fe 2 (PO 4 ) 3 (0<n≦3).
2. The process for producing lithium iron phosphate particles according to claim 1 , wherein each of the obtaining, the cooling, the pulverizing and the heating are carried out in the air or under oxidizing conditions with an oxygen partial pressure of higher than 0.21 and at most 1.0 atmosphere from 350 to 800° C.
3. The process for producing lithium iron phosphate particles according to claim 1 , wherein the valency of Fe in the crystals is +3-valent.
4. The process for producing lithium iron phosphate particles according to claim 1 , wherein the Li n Fe 2 (PO 4 ) 3 is Li 3 Fe 2 (PO 4 ) 3 .
5. The process for producing lithium iron phosphate particles according to claim 1 , wherein the rate of cooling the melt is at least 100° C./sec.
6. The process according to claim 1 , wherein the obtaining of the melt comprises:
mixing a Li 2 O source, a Fe 2 O 3 source and a P 2 O 5 source to obtain a material mixture; and
heating the material mixture to obtain the melt.
7. The process for producing lithium iron phosphate particles according to claim 6 , wherein the Li 2 O source is at least one member selected from the group consisting of lithium carbonate (Li 2 CO 3 ), lithium hydroxide (LiOH), lithium phosphate (Li 3 PO 4 ), lithium hydrogen phosphate (Li 2 HPO 4 ), lithium dihydrogen phosphate (LiH 2 PO 4 ), a hydrate of lithium carbonate (Li 2 CO 3 ), a hydrate of lithium hydroxide (LiOH), a hydrate of lithium phosphate (Li 3 PO 4 ), a hydrate of lithium hydrogen phosphate (Li 2 HPO 4 ), and a hydrate of lithium dihydrogen phosphate (LiH 2 PO 4 ).
8. The process for producing lithium iron phosphate particles according to claim 6 , wherein the Fe 2 O 3 source is at least one member selected from the group consisting of ferrous oxide (FeO), ferrosoferric oxide (Fe 3 O 4 ), ferric oxide (Fe 2 O 3 ), ferric oxyhydroxide (FeO(OH)), metal iron (Fe), ferric phosphate (FePO 4 ), ferrous phosphate (Fe 3 (PO 4 ) 2 ), ferric pyrophosphate (Fe 4 (P 2 O 7 ) 3 ), a hydrate of ferrous oxide (FeO), a hydrate of ferrosoferric oxide (Fe 3 O 4 ), a hydrate of ferric oxide (Fe 2 O 3 ), a hydrate of ferric oxyhydroxide (FeO(OH)), a hydrate of metal iron (Fe), a hydrate of ferric phosphate (FePO 4 ), a hydrate of ferrous phosphate (Fe 3 (PO 4 ) 2 ), and a hydrate of ferric pyrophosphate (Fe 4 P 2 O 7 ) 3 ).
9. The process for producing lithium iron phosphate particles according to claim 6 , wherein the P 2 O 5 source is at least one member selected from the group consisting of phosphorus pentoxide (P 2 O 5 ), phosphoric acid (H 3 PO 4 ), ammonium phosphate ((NH 4 ) 3 PO 4 ), ammonium phosphate, dibasic ((NH 4 ) 2 HPO 4 ), ammonium phosphate, monobasic (NH 4 H 2 PO 4 ), ferric phosphate (FePO 4 ), ferrous phosphate (Fe 3 (PO 4 ) 2 ), ferric pyrophosphate (Fe 4 (P 2 O 7 ) 3 ), a hydrate of phosphorus pentoxide (P 2 O 5 ), a hydrate of phosphoric acid (H 3 PO 4 ), a hydrate of ammonium phosphate ((NH 4 ) 3 PO 4 ), a hydrate of ammonium phosphate, dibasic ((NH 4 ) 2 HPO 4 ), a hydrate of ammonium phosphate, monobasic (NH 4 H 2 PO 4 ), a hydrate of ferric phosphate (FePO 4 ), a hydrate of ferrous phosphate (Fe 3 (PO 4 ) 2 ), and a hydrate of ferric pyrophosphate (Fe 4 (P 2 O 7 ) 3 ).
10. The process for producing lithium iron phosphate particles according to claim 6 , wherein the Fe 2 O 3 source is ferric oxide (Fe 2 O 3 ).
11. The process according to claim 1 , wherein the lithium iron phosphate particles have an average particle size of 10 nm to 5 μm.
12. The process according to claim 1 , wherein the lithium iron phosphate particles have a specific surface area of 0.5 to 200 m 2 /g.
13. A method for producing a secondary cell, said method comprising:
obtaining a melt containing, as represented by mol % based on oxides, from 1 to 50% of Li 2 O, from 20 to 50% of Fe 2 O 3 and from 30 to 60% of P 2 O 5 ;
cooling and solidifying the melt to obtain a solidified product;
pulverizing the solidified product to obtain a pulverized product;
heating the pulverized product in the air or under oxidizing conditions with an oxygen partial pressure of higher than 0.21 and at most 1.0 atmosphere from 350 to 800° C. to precipitate crystals of Li n Fe 2 (PO 4 ) 3 (0<n≦3); and
forming a secondary cell from a cathode material comprising the crystals.
14. The process according to claim 13 , wherein the obtaining of the melt comprises:
mixing a Li 2 O source, a Fe 2 O 3 source and a P 2 O 5 source to obtain a material mixture; and
heating the material mixture to obtain the melt.