In the crystallization system of the lithium hexafluorophosphate of the present invention, a first-stage crystallization kettle is connected to a lithium hexafluorophosphate mother liquor supply source through a lithium hexafluorophosphate mother liquor supply line; further connected to the lithium hexafluorophosphate mother liquor supply source through a mother liquor heat exchange line connected with a mother liquor heat exchanger; and further connected to a second-stage crystallization kettle through a first mother liquor delivery line configured to deliver lithium hexafluorophosphate mother liquor, a second-stage crystallization kettle is connected to a third-stage crystallization kettle through a second mother liquor delivery line configured to deliver lithium hexafluorophosphate mother liquor, a third-stage crystallization kettle is connected to a fourth-stage crystallization kettle through a crystalline particle delivery line configured to deliver small crystalline particles in the third-stage crystallization kettle; and further connected to a next process device through a first discharging line, and a fourth-stage crystallization kettle is connected to a next process device through a second discharging line. The crystallization system of lithium hexafluorophosphate of the present invention enables different crystallization stages to be carried out separately in different crystallization kettles, so as to realize continuous feeding and continuous discharging in the course of crystallization.

Disclosed are a process and continuous system for producing LiPF.sub.6, and a prepared mixture crystal, composition, electrolyte solution and lithium ion battery containing LiPF.sub.6. During preparation, a first feed stream containing PF5 and a second feed stream containing LiF and HF are introduced into a first microchannel reactor, a gas part of a product in the first microchannel reactor is introduced into a second microchannel reactor to react with a third feed stream containing LiPF.sub.6, LiF and HF, and a liquid part of the product in the first microchannel reactor is subjected to crystallization and drying to obtain LiPF.sub.6. The LiPF.sub.6 has the advantages of a high purity, a uniform particle size, a high product quality stability, etc., and is suitable for use as a component of an electrolyte solution of a lithium ion battery.