CN101195481A - Method for preparing high purity lithium hexafluorophosphate - Google Patents
Method for preparing high purity lithium hexafluorophosphate Download PDFInfo
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- CN101195481A CN101195481A CNA2006101368285A CN200610136828A CN101195481A CN 101195481 A CN101195481 A CN 101195481A CN A2006101368285 A CNA2006101368285 A CN A2006101368285A CN 200610136828 A CN200610136828 A CN 200610136828A CN 101195481 A CN101195481 A CN 101195481A
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- phosphorus pentafluoride
- lithium hexafluorophosphate
- phosphorus pentoxide
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Abstract
Provided is a process for preparing high-purity lithium hexafluorophosphate. The invention takes calcium fluorate and phosphorus pentoxide as raw materials to prepare phosphorus pentoxide with a dry method. High-purity nano lithium fluoride and phosphorus pentafluoride are employed to synthesize high-purity lithium hexafluorophosphate under compression with the dry method. Measuring according to the chemical reaction, phosphorus pentoxide excesses 10-60%, and the mixing time is 2-5 hours. Phosphorus pentoxide is synthesized by the gas protection (oxygen-free) reaction in a producer furnace of the phosphorus pentoxide with closed pressure, the reaction temperature is 200-340 DEG C, pressurized phosphorus pentoxide gas is introduced into a synthesis furnace of lithium hexafluorophosphate which is synthesized by heating under the gas protection (oxygen-free), the synthesis reaction temperature is 100-150 DEG C, the gas pressure is 1.0-2.0MPa, and the reaction time is 4.0-15 hours. The process of the invention employs no solvent, the process utilizes an all-dry method, the technique is simple, the producing process has no pollution for products, the products purity is high, and the industrialization implementation is convenient.
Description
Technical field
The present invention relates to a kind of preparation method of high purity lithium hexafluorophosphate.
Background technology is described
The battery that lithium ion battery is present consumption maximum, purposes is the widest; The worldwide production consumption reaches 2,000,000,000.China is lithium ion battery grown place the biggest in the world, and annual production breaks through 1,000,000,000.
Lithium hexafluoro phosphate is the main ionogen that present lithium ion battery is used; Nearly 1000 tons of present global solid lithium hexafluoro phosphate consumption; The consumption of China has also reached 500 tons.Expansion of using along with lithium-ion-power cell and manufacturing technology thereof perfect, the lithium hexafluoro phosphate consumption will have great increase.
Along with the fast development of China's lithium ion battery industry, various battery base mateirals progressively domesticize; Domesticly can produce positive electrode material, negative material, battery container, aluminium foil, Copper Foil etc. at present, but lithium hexafluoro phosphate (LiPF
6) because of its product purity requires high, dangerous big, difficult, the high reason of technical monopoly degree of raw material preparing of production, fail to make a breakthrough always.
Up to the present, solvent method is mainly used in the preparation of lithium hexafluoro phosphate, as Li Lingyun, and Zhang Zhi industry, Chen Xin is in chemical industry engineering 22 (3): 224 " the preparation technology's new developments of lithium hexafluoro phosphate " introduced.Investigators think synthesis of high purity LiPF
6Key be choice of Solvent; The solvent that has used has: anhydrous hydrogen fluoride, low alkyl oxide (as methyl ether, ether, glycol dimethyl ether, Propylene Glycol Dimethyl Ether and diglyme etc.), pyridine, acetonitrile, SO
2With carbonic ether etc.The main raw material that adopts is phosphorus pentafluoride, phosphorus pentachloride, lithium fluoride, lithium chloride etc.The most important thing is strictness control in the production to moisture.
Because the inherent characteristics of solvent method flow process, the product impurity of preparation is higher, separates purification difficult; Solvent method prepares the high purity lithium hexafluorophosphate long flow path, the operation conversion is numerous and use raw material many, and it is more to introduce impurity in the process; Produce simultaneously the equipment requirements height; Make product manufacturing cost height.In order to overcome these shortcomings, people take much count of the new preparation technology of exploitation high purity lithium hexafluorophosphate.
Summary of the invention
The purpose of this invention is to provide a kind of method with the synthetic high purity lithium hexafluorophosphate of dry process reaction.Solvent is not adopted in reaction, is easy to the product separation purifying.
The lithium hexafluoro phosphate of indication of the present invention is mainly as lithium ion battery electrolyte; It is characterized by: product is high-purity level, and foreign metal content is low, LiPF
6Content is greater than 99.9%, and the total impurities metal content is less than 50ppm; Water content is less than 10ppm; HF content is less than 50ppm.
It is raw material that the present invention adopts Calcium Fluoride (Fluorspan) and Vanadium Pentoxide in FLAKES, the dried preparation phosphorus pentafluoride; High-purity nano aluminium fluoride and phosphorus pentafluoride are depressed the synthetic high purity lithium hexafluorophosphate of dry method adding; The raw material high purity lithium fluoride is that the ammonium bifluoride with high-purity lithium chloride and vapor phase process production is raw material, the class sphere that adopts dry production, has the nanocrystalline agglomerate of mesoporous nano.It is characterized by:
(1) with industrial Calcium Fluoride (Fluorspan) and Vanadium Pentoxide in FLAKES in sealed ceramic matter ball milling mixing machine, ball milling mixes under the dry inert gas protection; Press the chemical reaction metering, Vanadium Pentoxide in FLAKES excessive 10～50%; Mixing time 2～5 hours.
(2) compound is loaded on fast in the lining molybdenum Stainless Steel Crucible and changes in the seal-off pressure process furnace (phosphorus pentafluoride producer); Mode by " vacuumize---inflation " is driven air in the burner hearth with dry inert gas; Reacting by heating is synthesized phosphorus pentafluoride; 200～340 ℃ of temperature of reaction; The gaseous state phosphorus pentafluoride is used for synthetic lithium hexafluoro phosphate through drawing pressurization;
(3) solid-state high-purity nano aluminium fluoride is used lining molybdenum Stainless Steel Crucible splendid attire in seal-off pressure process furnace (lithium hexafluoro phosphate synthetic furnace); Mode by " vacuumize---inflation " is driven air in the burner hearth with dry inert gas; Introduce the pressurization phosphorus pentafluoride gas, add the thermal synthesis lithium hexafluoro phosphate; 100～150 ℃ of synthesis reaction temperatures; Gaseous tension 1.0～2.0MPa; 4.0～15 hours reaction times.
(4) after reaction is finished, feed the dry inert gas carrier band and drive phosphorus pentafluoride, and the cooling material; Cooling back fast vacuum sealing packing.
Used dry inert gas is high pure nitrogen, high-purity argon gas in the process.
Advantage of the present invention: high purity lithium hexafluorophosphate purity height, HF content are low; With highly active nano-lithium fluoride is raw material, adopts absolutely dry method to prepare six hydrogen Trilithium phosphates, can control the moisture in the preparation process easily; Process does not adopt solvent, the absolutely dry method of process, and technology is simple, and production process is pollution-free to product, the product purity height; Industrialized implementation is convenient.
Embodiment
It below is part specific embodiment of the present invention.Providing of these embodiment limits the present invention anything but.
Embodiment 1
Industrial Calcium Fluoride (Fluorspan) and Vanadium Pentoxide in FLAKES are added in the sealed ceramic matter ball milling mixing machine by mass ratio weighing in 0.4: 1.0, and ball milling mixed 4 hours under argon shield; Be loaded on compound in the lining molybdenum Stainless Steel Crucible fast and change in the seal-off pressure process furnace A (phosphorus pentafluoride generation stove); Use lining molybdenum Stainless Steel Crucible splendid attire in seal-off pressure process furnace B (lithium hexafluoro phosphate synthetic furnace) solid-state high-purity nano aluminium fluoride; Drive air in stove A, the stove B burner hearth with high-purity argon gas; With 230 ± 5 ℃ of control stove A temperature, the gaseous state phosphorus pentafluoride is introduced the B stove through drawing pressurization, and 110 ± 5 ℃ of control B furnace temperatures, gaseous tension 1.8 ± 0.1MPa reacted 12 hours.After reaction is finished, feed the high-purity argon gas carrier band and drive phosphorus pentafluoride, and the cooling material; Cooling back fast vacuum sealing packing.
Embodiment 2
Industrial Calcium Fluoride (Fluorspan) and Vanadium Pentoxide in FLAKES are added in the sealed ceramic matter ball milling mixing machine by mass ratio weighing in 0.3: 1.0, and ball milling mixed 3 hours under the dry inert gas protection; Be loaded on compound in the lining molybdenum Stainless Steel Crucible fast and change in the seal-off pressure process furnace A (phosphorus pentafluoride generation stove); Use lining molybdenum Stainless Steel Crucible splendid attire in seal-off pressure process furnace B (lithium hexafluoro phosphate synthetic furnace) solid-state high-purity nano aluminium fluoride; Drive air in stove A, the stove B burner hearth with high-purity argon gas; 320 ± 5 ℃ of control stove A temperature, the gaseous state phosphorus pentafluoride is introduced the B stove through drawing pressurization, and 140 ± 5 ℃ of control B furnace temperatures, gaseous tension 1.2 ± 0.1MPa reacted 8 hours.After reaction is finished, feed the high-purity argon gas carrier band and drive phosphorus pentafluoride, and the cooling material; Cooling back fast vacuum sealing packing.
Embodiment 3
As condition as described in the embodiment 1, changing phosphorus pentafluoride, to generate stove A temperature be 320 ± 5 ℃, the preparation lithium hexafluoro phosphate.
Embodiment 4
As Calcium Fluoride (Fluorspan) and the mixing condition of Vanadium Pentoxide in FLAKES and the formation condition of phosphorus pentafluoride as described in the embodiment 1, the synthesis condition that changes lithium hexafluoro phosphate is 140 ± 5 ℃ of B furnace temperatures, gaseous tension 1.2 ± 0.1MPa, reacts 6 hours; The preparation lithium hexafluoro phosphate.
Embodiment 5
As condition as described in the embodiment 2, changing phosphorus pentafluoride, to generate stove A temperature be 280 ± 5 ℃, the preparation lithium hexafluoro phosphate.
Embodiment 6
As Calcium Fluoride (Fluorspan) and the mixing condition of Vanadium Pentoxide in FLAKES and the formation condition of phosphorus pentafluoride as described in the embodiment 2, the synthesis condition that changes lithium hexafluoro phosphate is 110 ± 5 ℃ of B furnace temperatures, gaseous tension 1.8 ± 0.1MPa, reacts 14 hours; The preparation lithium hexafluoro phosphate.
Truth example 7
Industrial Calcium Fluoride (Fluorspan) and Vanadium Pentoxide in FLAKES are added in the sealed ceramic matter ball milling mixing machine by mass ratio weighing in 0.35: 1.0, and ball milling mixed 4 hours under the dry inert gas protection; Be loaded on compound in the lining molybdenum Stainless Steel Crucible fast and change in the seal-off pressure process furnace A (phosphorus pentafluoride generation stove); Use lining molybdenum Stainless Steel Crucible splendid attire in seal-off pressure process furnace B (lithium hexafluoro phosphate synthetic furnace) solid-state high-purity nano aluminium fluoride; Drive air in stove A, the stove B burner hearth with high-purity argon gas; 280 ± 5 ℃ of control stove A temperature, the gaseous state phosphorus pentafluoride is introduced the B stove through drawing pressurization, and 120 ± 5 ℃ of control B furnace temperatures, gaseous tension 1.5 ± 0.1MPa reacted 10 hours.After reaction is finished, feed the high-purity argon gas carrier band and drive phosphorus pentafluoride, and the cooling material; Cooling back fast vacuum sealing packing.
By last embodiment, product all reaches the lithium ion battery service requirements, and quality reaches: LiPF
6Content is greater than 99.9%, and the total impurities metal content is less than 50ppm; Water content is less than 10ppm; HF content is less than 50ppm.
Claims (3)
1. the preparation method of a high purity lithium hexafluorophosphate is characterized in that may further comprise the steps:
(1) with Calcium Fluoride (Fluorspan) and Vanadium Pentoxide in FLAKES in sealing ball milling mixing machine, ball milling mixes under the dry inert gas protection; Press the chemical reaction metering, Vanadium Pentoxide in FLAKES excessive 10～50%; Mixing time 2～5 hours;
(2) be loaded on compound in the crucible and change in the seal-off pressure phosphorus pentafluoride producer; Mode by " vacuumize---inflation " is driven air in the burner hearth with dry inert gas; Reacting by heating is synthesized phosphorus pentafluoride; 200～340 ℃ of temperature of reaction; The gaseous state phosphorus pentafluoride is used for synthetic lithium hexafluoro phosphate through drawing pressurization;
(3) use the crucible splendid attire in seal-off pressure lithium hexafluoro phosphate synthetic furnace solid-state high-purity nano aluminium fluoride; Mode by " vacuumize---inflation " is driven air in the burner hearth with dry inert gas; Introduce the pressurization phosphorus pentafluoride gas, add the thermal synthesis lithium hexafluoro phosphate; 100～150 ℃ of synthesis reaction temperatures; Gaseous tension 1.0～2.0MPa; 4.0～15 hours reaction times;
(4) after reaction is finished, feed the dry inert gas carrier band and drive phosphorus pentafluoride, and the cooling material; Cooling back fast vacuum sealing packing.
2. the preparation method of high purity lithium hexafluorophosphate according to claim 1 is characterized in that described dry inert gas is high pure nitrogen or high-purity argon gas.
3. the preparation method of high purity lithium hexafluorophosphate according to claim 1 is characterized in that described crucible is lining molybdenum Stainless Steel Crucible.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2006101368285A CN101195481A (en) | 2006-12-08 | 2006-12-08 | Method for preparing high purity lithium hexafluorophosphate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275894A (en) * | 2011-05-23 | 2011-12-14 | 中南大学 | Method for preparing lithium hexaflourophosphate |
| CN102381695A (en) * | 2011-07-28 | 2012-03-21 | 成都牧甫生物科技有限公司 | Preparation method of lithium hexafluorophosphate |
| CN102491305A (en) * | 2011-11-24 | 2012-06-13 | 山东省智能光电新能源研究院 | Method for preparing lithium hexafluorophosphate by using composite solvent |
| CN102976303A (en) * | 2012-12-12 | 2013-03-20 | 四川大学 | Method for preparing lithium hexafluorophosphate |
| CN103232072A (en) * | 2013-04-12 | 2013-08-07 | 北京石磊乾坤含氟新材料研究院有限责任公司 | Synthetic method of lithium hexafluoroferrate and new purpose thereof |
| CN103253641A (en) * | 2012-02-16 | 2013-08-21 | 湖北诺邦化学有限公司 | Solid phase method for preparation of high purity phosphorus pentafluoride gas |
| CN103466589A (en) * | 2013-08-29 | 2013-12-25 | 中国海洋石油总公司 | Preparation method of high-purity lithium hexafluorophosphate |
| CN106241840A (en) * | 2016-09-08 | 2016-12-21 | 甘肃立焘新能源科技发展有限公司 | The preparation method of a kind of lithium hexafluoro phosphate and preparation system |
-
2006
- 2006-12-08 CN CNA2006101368285A patent/CN101195481A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275894A (en) * | 2011-05-23 | 2011-12-14 | 中南大学 | Method for preparing lithium hexaflourophosphate |
| CN102381695A (en) * | 2011-07-28 | 2012-03-21 | 成都牧甫生物科技有限公司 | Preparation method of lithium hexafluorophosphate |
| CN102491305A (en) * | 2011-11-24 | 2012-06-13 | 山东省智能光电新能源研究院 | Method for preparing lithium hexafluorophosphate by using composite solvent |
| CN103253641A (en) * | 2012-02-16 | 2013-08-21 | 湖北诺邦化学有限公司 | Solid phase method for preparation of high purity phosphorus pentafluoride gas |
| CN103253641B (en) * | 2012-02-16 | 2014-12-17 | 湖北诺邦化学有限公司 | Solid phase method for preparation of high purity phosphorus pentafluoride gas |
| CN102976303A (en) * | 2012-12-12 | 2013-03-20 | 四川大学 | Method for preparing lithium hexafluorophosphate |
| CN103232072A (en) * | 2013-04-12 | 2013-08-07 | 北京石磊乾坤含氟新材料研究院有限责任公司 | Synthetic method of lithium hexafluoroferrate and new purpose thereof |
| CN103232072B (en) * | 2013-04-12 | 2015-04-22 | 北京石磊乾坤含氟新材料研究院有限责任公司 | Synthetic method of lithium hexafluoroferrate and purpose thereof |
| CN103466589A (en) * | 2013-08-29 | 2013-12-25 | 中国海洋石油总公司 | Preparation method of high-purity lithium hexafluorophosphate |
| CN103466589B (en) * | 2013-08-29 | 2015-12-02 | 中国海洋石油总公司 | A kind of preparation method of high purity lithium hexafluorophosphate |
| CN106241840A (en) * | 2016-09-08 | 2016-12-21 | 甘肃立焘新能源科技发展有限公司 | The preparation method of a kind of lithium hexafluoro phosphate and preparation system |
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Open date: 20080611 |