TW389742B - Lithium fluorophosphates and process for producing same - Google Patents

Description

‘Annex No. 861 14398 Patent Application ^ 'ea'3.f 5' Chinese Manual Revised Page a7 Revised March 1988 B7

V. Description of the invention (5) 0 CFj ^ P ^ —F Li ’F F

(VIII) (Please read the notes on the reverse side before filling out this page) Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs (IX) As a conductive salt in electrolytes, the electrolyte includes these lithium salts, and also about A lithium battery containing the compound as a conductive salt. In order to make the salts of the present invention, in the first step, the appropriate monochloro- or fluoro-, dichloro- or difluoro-, chlorofluoroalkylphosphane, chloromono-, chloro-di, chloro Trinity, or chlorotetraalkylphosphorane, fluoromono, fluorodione, fluorotri- or fluorotetraalkylphosphorane or trifluoromonohydroalkylphosphorane are dissolved in the solvent and at normal pressure and -1 5 to Electrochemical fluorination is performed in a known manner at a temperature of 20 ° C. Hydrogen fluoride is suitable as a solvent for the reaction. The fluorination reaction is terminated when 90-150%, especially 110-1 3 5% of the theoretical power has been consumed. This is measured by a coulometric method. Depending on the reaction time, a product mixture is obtained which includes both fully saturated compounds and partially fluorinated compounds. For example, the paper size of the following products applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -8-Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 _B7_ V. Description of the invention (1) The Department of the Invention Regarding the novel lithium fluorophosphate Li + CPF of the general formula: (CHbFc (CF3) d) e] -CI] where a is 1, 2, 3, 4 or 5, b is 0 or 1, and c is 0, 1, 2, or 3, d is 0, 1, 2, or 3, and e is 1, 2, 3, or 4, provided that if the ligands (CHbF. (CF3) d) may be different, then the total a + The total number of e is 6 ′ b + c + d is 3 and b and c are not 0 at the same time. Regarding a method for manufacturing the compound, its use as an electrolyte and the use of a lithium battery made with the electrolyte. The present invention also relates to compounds of the following general formula [PF a (CHbFc (CFs) a) e) [la]. · 'F where, as shown in formula (I), b is 0 or 1, and c is 0, 1, 2 or 3, d is 0, 1, 2 or 3 and e is 1, 2, 3 or 4, but this paper size uses the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the note on the back first Please fill in this page again for matters) * 1Τ -4-/ -----------Revise Lin Kui.::1 «A7 B7 Printed by Shellfish Consumer Cooperative of Intellectual Property Bureau of Ministry of Economic Affairs 8) Experiments have shown that these compounds are extremely stable. When stored dry in a solid state, the perfluorinated compound showed no decomposition at a temperature below 100 ° C. It proves that even further increasing the temperature is thermally stable. Only a slight discoloration is exhibited at temperatures exceeding 130 ° C. "Even when stored in solution, such as dimethoxyethane, no color change was observed, or no decomposition products were found even after several weeks . In this regard, the compounds according to the present invention, in particular the compounds of the formulae I I, IV, V, V I and VI I, are already well-suited as conductive salts in non-aqueous electrolytes used in lithium batteries. In addition, electrolytes containing these compounds have significant chemical and electrochemical stability. In particular, the oxidation of the corresponding anion cannot be detected before lithium precipitation. Such an electrolyte includes, in addition to an organic lithium salt, for example, a compound of the formula (I) of the present invention, one or more non-aqueous based solvents, and optionally further additives. If necessary, in addition to those of the present invention, a known lithium salt may be added to the electrolyte as a conductive salt. Further details of the structure or operating mode of such electrolytes and lithium batteries are known to those skilled in the art. The compound of the present invention can be used in a manner completely similar to a lithium compound known for this use, and exhibits extremely high stability under these conditions. Corresponding batteries exhibit excellent properties with respect to capacity and constant voltage and also exhibit unlimited usage power above the average number of charge-discharge cycles described above. , t The following examples are provided to provide a better illustration of the present invention, but r — lv ^ ------------ order --------- line. (Please Please read the notes on the back of the page before filling in this page.) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -11-A7 B7 V. Description of the invention (2) a is 1, 2, 3 Or 4, it needs to be used as an intermediate product to produce a compound of formula (I). Generally, lithium hexafluorophosphate is used as a salt in a conductive lithium secondary battery. The disadvantage is that the salt is relatively low in hydrolysis resistance, so various experiments were performed to find alternatives to the salt. For example, W 0 8 8/0 3 3 3 1 describes cycloperfluoroalkane bis (sulfosyl) glucosamine, and also includes its lithium salt, which can be used as a non-aqueous electrolyte for conductive lithium secondary batteries. Of salt. However, as shown by experiments, such compounds may have to be produced at great expense, and undesired by-products must be released after synthesis. Since renewable properties are indispensable for use as a battery electrolyte component, purification of salts is essential. It is therefore an object of the present invention to provide a conductive salt of an electrolyte used in a lithium battery. The object of the present invention is also to provide a method by which the conductive salt of the present invention can be easily and inexpensively produced. The purpose of the present invention is to achieve the economy through the novel fluorophosphate k compounds of the following general formula: ni—ϋ t ^ — n I nn I-.r_ \. (Please read the note on the back before filling this page) The Central Government Bureau of the People ’s Republic of China ’s Employees ’Cooperatives’ Cooperative Seal 簟 b Η \ 1 / d Among them, or ,, 1 ο ο ο Yes Yes Is abed or or is the same as this paper standard (CNS) A4 specification ( 210X297 mm)

A A7 B7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives (10) 0.53 amps per square inch of electrolytic operation at a current consumption of 4 20 amp-hours (131% of theoretical 收集), collected about 220 from the battery Gram of liquid product ends thereafter. After the temperature had been adjusted to 20 ° C and the lower phase had been separated from the hydrogen fluoride phase, 18 g of the original product was obtained. Here, 75% bis (heptafluoroisopropyl) trifluorophosphine (Ila) and 15% heptafluoroisopropyl (1,1,1,3,3,3-hexafluoroisopropyl) can be measured by NMR19F spectrum. Propyl) trifluorophosphorane (I lb) and bis (hexa-1,1'1,3,3,3-hexafluoroisopropyl) trifluorophosphorane (I Ic). This mixture can be separated into Each includes a fraction of one of these compounds as the main component. In addition, after separation of the hydrogen fluoride phase, 33 g of a low product which was liquid at room temperature was obtained from the cooled-down retention. Studies of the NMR 1 9 F spectrum indicate that these are mainly heptafluoroisopropyltetrafluorophosphine (lid), 1,1,1,3,3,3-hexafluoroisopropyltetrafluorophosphine (II e ) And octafluoropropane. Octafluoropropane can be distilled off by heating to 20 ° C. The residue can be separated by fractionation to include heptafluoroisopropyltetrafluorophosphine (II d) or 1,1,1,3,3,3-hexafluoroisopropyltetrafluorophosphine (II e) as the main group Fractions. The obtained compound can be characterized by the following data: Bis (heptafluoroisopropyl) trifluorophosphorane (I la): • n ^ * 1 ^ n .. · 1 · 1 I · 1 1_ · I f ^ n ^ nn (Please read the precautions on the back before filling this page) Order --------- line. This paper size applies to Chinese national standard (CNS > A4 specification (210 X 297 mm) -13- Α7 Β7 V. Description of the invention (3) e is 1, 2, 3 or 4, provided that if the ligands (CHbFe (CF3) d) may be different, then the total a + e is equal to 6, b + c + d The total is equal to 3 and b and c are not 0 at the same time. Lithium fluorophosphate can replace traditional lithium hexafluorophosphate, which is used as a conductive salt in lithium secondary batteries, and can also be mixed with the latter. Therefore, the present invention relates to ) Of the present invention is also novel and also relates to a method for producing a compound of the general formula (I a), CPF. (CHbFc CCF3) d) e) [la] wherein, as shown in formula (I), b is 0 or 1, c is 0, 1, 2, or 3, d is 0, 1, 2, or 3, and e is 1, 2, 3, or 4, but printed by the Zhengong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Read the note on the back and fill in this page) a is 1, 2, b or 4, which needs to be used as an intermediate to produce the compound of formula (I). Finally, the present invention also relates to an electrolyte including the salt according to the present invention including the salt of the present invention and an electrochemical cell prepared using the electrolyte. Such an electrochemical battery may not be a primary battery, or it may be a secondary battery including a lithium compound according to Chemical Formula (I). The present invention is particularly related to the following lithium salts. The paper size is in accordance with China National Standard (CNS) A4 (210X297 mm).

V. Description of the invention (15) J 1 P, F = 10.03.0 Hz J 2 P, F = 122.0 Hz (Please read the precautions on the back before filling this page) Example 3 Bis (Heptafluoroisopropyl) Lithium (II) tetrafluorophosphate Slowly add 12 g (0.028 mol) of diheptafluoroisopropyl) trifluorophosphorane (II a) into the PTFE reaction vessel while stirring with a magnetic stirrer without moisture. The solution was composed of 0.82 g (0.031 mol) of LiF and 60 ml of pre-dried dimethoxyethane, and the temperature was maintained at room temperature by cooling in an ice water bath. It was then stirred at the same temperature for one hour | and a small amount of metallic lithium was added. The reaction mixture was kept at room temperature for 24 hours, then filtered and used immediately as an electrolyte for a rechargeable battery. However, lithium bis (heptafluoroisopropyl) lithium tetrafluorophosphate (II) formed during the reaction can also be isolated by distilling off the solvent under high vacuum. Lithium complex salt (II), L i + [i— C3F7) 2PF4) x2DME is isolated, printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Bei 1 Consumer Cooperative, Melting point: 126 — 128 °; up to 130 ° C is still thermally stable. Analysis Li: Theoretical 値: 0.93% Actual 値: 1.15%

The solvent can be heated by heating the complex salt (I I

I remove it for several days. -18- The size of this paper applies to China® Home Standard (CNS) A4 (210 X 297 mm) V. Description of the invention (4)

CF3 f F s \ / / CF-P——CF b) c) d) A7 B7

Li, (II) CF "F, / Corpse, CF-P-CH cf! / \ Ncf,, F, / Strict CH-P-CH 〆%, CF, \ / CjPs—Ρς — f c2f5 U · and ( Ml) I IΓ n Jr I ni IJ, 11 (Please read the notes on the back before filling in this page) II 'u * Order (IV) Printed by the Shellfish Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs e)

FF \ / CF; —P-CF, S / \ * FFU, this paper size applies to China National Standard (CNS) A4 specification (210X297 mm >. (V) (VI) 'Annex No. 861 14398 Patent Application Case ^ 'ea'3.f 5' Chinese manual amendment page a7 March 1998 amendment B7

V. Description of the invention (5) 0 CFj ^ P ^ —F Li ’F F

(VIII) (Please read the notes on the reverse side before filling out this page) Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs (IX) As a conductive salt in electrolytes, the electrolyte includes these lithium salts, and also about A lithium battery containing the compound as a conductive salt. In order to make the salts of the present invention, in the first step, the appropriate monochloro- or fluoro-, dichloro- or difluoro-, chlorofluoroalkylphosphane, chloromono-, chloro-di, chloro Trinity, or chlorotetraalkylphosphorane, fluoromono, fluorodione, fluorotri- or fluorotetraalkylphosphorane or trifluoromonohydroalkylphosphorane are dissolved in the solvent and at normal pressure and -1 5 to Electrochemical fluorination is performed in a known manner at a temperature of 20 ° C. Hydrogen fluoride is suitable as a solvent for the reaction. The fluorination reaction is terminated when 90-150%, especially 110-1 3 5% of the theoretical power has been consumed. This is measured by a coulometric method. Depending on the reaction time, a product mixture is obtained which includes both fully saturated compounds and partially fluorinated compounds. For example, the paper size of the following products applies to the Chinese National Standard (CNS) A4 (210X297 mm) -8-Printed by A7 B7, Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (6) is based on chlorine Obtained in the fluorination reaction of di'isopropylphosphane: a), f, / F

CF-P-CF I CF, (丨 la) b) CF "F, Corpse 3

• CF — P ~ " CH • cf3 f cf3, (lib) C), F, / corpse 3

CH —P—CH CF’3 丨 cp3 (Me) d) cf3 f /

CF-P cf3 / (lid) e) 5 F, /

CH-P CF; F7 XF ((lie) The actual salts of the chemical formula (I) of the present invention are obtained by dissolving the fluorinated alkylphosphorane product mixture obtained in the first stage in an anhydrous condition, suitably aprotic, Polar solvents (such as dimethyl ether, dimethoxyethane, or mixtures thereof) and depending on the reactivity-3 5 to 60 ° C 'preferably at room temperature (please read the notes on the back before filling in (This page)

This paper size applies Chinese National Standard (CNS) A4 Zhuge (210 X 297 mm) -9-Printed by A7 B7, Shellfish Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs 5. Description of the invention (7) Lithium fluoride at temperature It is obtained by reacting to form a compound of formula (I). According to the electrolyte of the present invention, a pure compound of formula (I) and those obtained by a fluorination reaction can be used. Because of the reproducibility of degrading properties, it is best to use pure compounds to make those electrolyte solutions. Surprisingly, it has been found experimentally that compounds of formula (I) are resistant to hydrolysates in polar solvents at room temperature. In conclusion, Those compounds', especially those whose alkyl groups are completely saturated with fluorine. In this regard, the hydrolysis resistance increases with the number of fluorine atoms in the molecule. Aprotic polar solvents should refer to the solvents listed below, such as mononitrile acetonitrile or benzonitrile, monoether diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane or dimethyltetrahydrofuran Monoesters are methyl or ethyl esters of formic acid, acetic acid, propionic acid, and cyclic esters such as butyrolactone, and organic carbonates such as dimethyl carbonate, diethyl carbonate, ethyl carbonate Methyl methyl ester, ethylene carbonate or propylene carbonate, monomethylamine diΦmethylformamide 'diethylmethylglucosamine, N-methylpyrrolidine or dimethylsulfinate, diethyl Methylene mill 'tetramethylene mill or other sulpholanes. In addition, the salts of the present invention have excellent solubility in solvents, and especially those compounds saturated with fluorine have very little hygroscopicity. 9 This paper is sized for China National Standard (CNS) A4 (210X297 mm) (锖 Please read the precautions on the back before filling this page) Order / -----------Revise Lin Gui.::1 «A7 B7 Printed by the Shellfish Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Description of the Invention (8) Experiments have shown that these compounds are extremely stable. When stored dry in a solid state, the perfluorinated compound showed no decomposition at a temperature below 100 ° C. It proves that even further increasing the temperature is thermally stable. Only a slight discoloration is exhibited at temperatures exceeding 130 ° C. "Even when stored in solution, such as dimethoxyethane, no color change was observed, or no decomposition products were found even after several weeks . In this regard, the compounds according to the present invention, in particular the compounds of the formulae I I, IV, V, V I and VI I, are already well-suited as conductive salts in non-aqueous electrolytes used in lithium batteries. In addition, electrolytes containing these compounds have significant chemical and electrochemical stability. In particular, the oxidation of the corresponding anion cannot be detected before lithium precipitation. Such an electrolyte includes, in addition to an organic lithium salt, for example, a compound of the formula (I) of the present invention, one or more non-aqueous based solvents, and optionally further additives. If necessary, in addition to those of the present invention, a known lithium salt may be added to the electrolyte as a conductive salt. Further details of the structure or operating mode of such electrolytes and lithium batteries are known to those skilled in the art. The compound of the present invention can be used in a manner completely similar to a lithium compound known for this use, and exhibits extremely high stability under these conditions. Corresponding batteries exhibit excellent properties with respect to capacity and constant voltage and also exhibit unlimited usage power above the average number of charge-discharge cycles described above. , t The following examples are provided to provide a better illustration of the present invention, but r — lv ^ ------------ order --------- line. (Please Please read the notes on the back of the page before filling in this page.) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -11-A7 ___B7_ 5. Description of the invention (9). Features of the invention. EXAMPLES Example 1 Bis (heptafluoroisopropyl) trifluorophosphine (Ila) and its derivative diisopropylchlorophosphane were electrochemically fluorinated in an electrochemical cell including hydrogen fluoride as a solvent by the Simons method.化 反应。 Reaction. A cylindrical battery system with a volume of 3 10 cubic centimeters was used to provide a nickel anode with an effective surface area of S = 3.75 square inches and a cathode with the same effective surface area. In addition, the battery is provided with a cooled condenser. During the electrolysis, the battery temperature was maintained at 5 ° C and the condenser was maintained at 30 ° C. i- II l · — nni I (-· I (Please read the precautions on the back before filling this page) Order the Central Consumers' Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives to print and dissolve 5 7 grams in 200 grams of hydrofluoric acid Of diisopropylchlorophosphine was added in 2 3 5 grams of previously electrolyzed hydrofluoric acid, and it was stated that it was performed as follows = electrolysis time [ampere-hour] amount of diisopropylchlorophosphine 〔G〕 0 10 7 8-1 1 0 15 7.4 10 2 3 0-6 10 2 9 4.0 10 3 6 5.2 7 Cool the gas product that has passed through the cooling condenser and two PTFE trapped gases to 7 8 ° C Will use the voltage of 4. 4-5. 4 volts and current density of 30. -12-This paper size uses China National Standards (CNS) A4 Zhuge (2 丨 0X297 mm) repair girl- -----

A A7 B7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives (10) 0.53 amps per square inch of electrolytic operation at a current consumption of 4 20 amp-hours (131% of theoretical 收集), collected about 220 from the battery Gram of liquid product ends thereafter. After the temperature had been adjusted to 20 ° C and the lower phase had been separated from the hydrogen fluoride phase, 18 g of the original product was obtained. Here, 75% bis (heptafluoroisopropyl) trifluorophosphine (Ila) and 15% heptafluoroisopropyl (1,1,1,3,3,3-hexafluoroisopropyl) can be measured by NMR19F spectrum. Propyl) trifluorophosphorane (I lb) and bis (hexa-1,1'1,3,3,3-hexafluoroisopropyl) trifluorophosphorane (I Ic). This mixture can be separated into Each includes a fraction of one of these compounds as the main component. In addition, after separation of the hydrogen fluoride phase, 33 g of a low product which was liquid at room temperature was obtained from the cooled-down retention. Studies of the NMR 1 9 F spectrum indicate that these are mainly heptafluoroisopropyltetrafluorophosphine (lid), 1,1,1,3,3,3-hexafluoroisopropyltetrafluorophosphine (II e ) And octafluoropropane. Octafluoropropane can be distilled off by heating to 20 ° C. The residue can be separated by fractionation to include heptafluoroisopropyltetrafluorophosphine (II d) or 1,1,1,3,3,3-hexafluoroisopropyltetrafluorophosphine (II e) as the main group Fractions. The obtained compound can be characterized by the following data: Bis (heptafluoroisopropyl) trifluorophosphorane (I la): • n ^ * 1 ^ n .. · 1 · 1 I · 1 1_ · I f ^ n ^ nn (Please read the notes on the back before filling out this page) Order --------- line. This paper size applies to Chinese national standard (CNS > A4 specification (210 X 297 mm) -13- Economy Printed by the Central Standards Bureau of the Ministry of Work and Consumer Cooperatives A7 B7 V. Description of the invention (11) N MR 19F, part per million: (using a CD3CN film with CC13F as the standard) -39.72dtm (3F1) -70. 1 5 m (1 2 F 3) -171.78dm (2F2) J 3 FiF2 = 8.0 Hz NMR 31P, one part per million: (using a CD3CN film with 85% H3P04 as standard) — 2 6. 0 qtm J 1 Hz J 2 P, F2 = 102 Hz J 3 P, F3 = 4.9 Hz Heptafluoroisopropyl (1,1,1,3,3,3-hexafluoroisopropyl) trifluorophosphorane (II b) : CFi FF CF3 CF ~~ 〒CH CF \ CF3 f cf3 • (lib) NMR 19F, part per million: (using a CD3CN film with CC13F as standard) —33. 1 0 dtm (3 F 1)- 59 56m (6F4) -7〇.26dm (6F3) -171.90dm (lF2) (Please read the note on the back first Please fill in this page again) The size of the paper is applicable to China National Standards (CNS) A4 (210X297mm) -14-CD 3 CN film printed by Beige Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs As standard) — 2 3 · 2 qtm J 1 ρ, F 1 = = 1 0 1 4. 0 Hz J 2 ρ, p 2 = = 9 9 .0 Hz J 3 ρ, p 3 = = 5. 2 Hz J 3 Ρ, F 4 = = 5 · 7 Hz J 2 ρ, H = 11.0 Hz NM R 1 H, one millionth: (with a CD 3 C Ν film as standard) 3.9 dm double (Six one 1, 1, 1 * 3 * 3, 3-fluorophosphane (II c) CF 3 FVVF cf3 > r I —CH CF 1 3 F \ cf3 A7 B7 V. Description of the invention (12) NMR 31P, parts per million One: (with 85% (lie) NMR 19F, one millionth: (with true CClaF CD 3 CN film as a standard) -25.96dm (3F ') -59.51m (12F4) NMR 31P, hundred One ten-thousandth: (using a CD3CN film with 85% H3P04 as the standard) — 2 0 · 6 9 Q in This paper size applies to China National Standard (CNS) A4 (210X297 mm) ^ H ^ J ^ I / ^ * * (1W first talk about the back Notes on this page) _ {\ -15- Printed by A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (13) Hertz J 3 P, F2 = 11.3 Hertz NMR 1Η, one millionth: CD3CN film with TMS as standard) 3.9dm heptafluoroisopropyltetrafluorophosphorane (II d): CF. CF, FF CF "〆

Old)

NMR 19F, part per million: ((using CD3CN film with CC13F as standard); -30 ° C) -50.10dm (4F1) -72-22m (6F3) -172.83dm (lF2) NMR 31P, million One part: ((using CD3CN film with 85% H3P04 as standard);-40 ° C 5

3 P D S E P 1 d-F1, 1042.0 Hz F 2 = 1 0. 0 Hz 2 3

P P P

F 6.0. 0 Hz ^ ^ (Vi (please read the precautions on the back before filling in this page) 1,1,1 lie) 3,3,3 —Hexafluoroisopropyltetrafluorophosphine This paper is applicable to China Standard (CNS) Α4 Zhuge (210X297 mm) -16-V. Description of the invention (14) CF, FF, \ f CH-P. CF,

I

F A7 B7 (He) NMR 19F, one part per million: ((using a CD3CN film with CClsF as a standard);-30 ° C) -40. 90dm (4F1)-61 · 8m (6F4) NMR 31P, 1 part per million: ((with 85% H3P〇4 & CD3COCD3 film as standard); -4 0 t) (Please read the note on the back before filling this page) Central Bureau of Standards of the Ministry of Economy β; Example 2 printed by the Industrial and Commercial Cooperative Co., Ltd.) Difluorophosphane (Va) was prepared according to a similar procedure as in Example 1 咋. 70 g of tris (pentafluoroethyl) difluorophosphine was prepared from 69 g of triethylphosphine oxide (Va) ° NMR 31P spectral numbers are consistent with those described in the literature (V. J. Semenii et al .; Zh. Obshch. Khim. (Russ.) 1985, Vo I. 55; 12, 2716-2720): cf, . CF.

F, (Va) NMR 31P, (using a CD3C0CD3 film with 85% H3po4 as the standard), 17.5 parts per million -47.5 se ρ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm ) · Ϊ́τ -17-

V. Description of the invention (15) J 1 P, F = 10.03.0 Hz J 2 P, F = 122.0 Hz (Please read the precautions on the back before filling this page) Example 3 Bis (Heptafluoroisopropyl) Lithium (II) tetrafluorophosphate Slowly add 12 g (0.028 mol) of diheptafluoroisopropyl) trifluorophosphorane (II a) into the PTFE reaction vessel while stirring with a magnetic stirrer without moisture. The solution was composed of 0.82 g (0.031 mol) of LiF and 60 ml of pre-dried dimethoxyethane, and the temperature was maintained at room temperature by cooling in an ice-water bath. It was then stirred at the same temperature for one hour | and a small amount of metallic lithium was added. The reaction mixture was kept at room temperature for 24 hours, then filtered and used immediately as an electrolyte for a rechargeable battery. However, lithium bis (heptafluoroisopropyl) lithium tetrafluorophosphate (II) formed during the reaction can also be isolated by distilling off the solvent under high vacuum. Lithium complex salt (II), L i + [i— C3F7) 2PF4) x2DME is isolated, printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Bei 1 Consumer Cooperative, Melting point: 126 — 128 °; up to 130 ° C is still thermally stable. Analysis Li: Theoretical 値: 0.93% Actual 値: 1.15%

The solvent can be heated by heating the complex salt (I I

I remove it for several days. -18- This paper size is in accordance with China® Home Standard (CNS) A4 (210 X 297 mm) Printed on A7 B7 by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 5. Description of the invention (16) Example 3 a In order to manufacture The lithium salt of the present invention and the fluorophosphane mixture obtained in Example 1 can be used directly without first fractionating. 16 g of the fluorophosphorane mixture from Example 1 above comprising 7 5% of the compound (II a), 15% of the compound (lib) and 10% of the compound (I Ic) was added, from 1.0 g of LiF and 80 ml A solution consisting of dry DME. This solution can also be used directly as an electrolyte after filtration. However, if pre-dried hexane is added to the DME solution, the Li salt can also be crystallized from the solution. 1 3.6 grams of bis (heptafluoroisopropyl) lithium tetrafluorophosphate (II) and 6% heptafluoroisopropyl (1,1'1,3,3,3-hexafluoroisopropyl) -tetrafluoro Lithium (IV) phosphate is obtained by recrystallizing the obtained product from a solvent mixture consisting of dry DME and dibutyl ether (1: 2). The structures of the salts (II) and (III) were detected by N M R 19F and 31P spectra. NMR spectra were measured in a CD3COCD3 solution with CC 13F. If not, then 8 5% H3P04 was used as the external standard. Bis (heptafluoroisopropyl) lithium (II) tetrafluorophosphate NMR 19F, one millionth: -58.14dm (4F1) -71.07m (12F3) —184 · 4〇dpsep (2F2) Applicable to this paper China National Standards (CNS) A4 (210X297 mm) -19-(Please read the precautions on the back before filling out this page) Order A7 A7 Employees ’Cooperative Cooperatives’ Seal B7 of the Central Bureau of Economic Affairs ) -l'71 · 90dm (IF2) J 3 Hz J 4 F'Fs ^ lO.g Hz J 3 F2, F3 = 4.7 Hz NMR 31P, part per million: -149 · 27ptm -148. 42p tm ( CD3. CN solution) J 1 P > F1 = 943.0 Hz J 2 P-F2 = 75.0 Hz J 3 P, F3 = 8.2 Hz heptafluoroisopropyl (1, 1, 1, 1, 3, 3, 3_hexafluoro Isopropyl) lithium (III) tetrafluorophosphate NMR 19F, part per million: -47. 20dddm (4F ') -58.01dpd (6F4) -7〇.79pdd (6F3) -183 · 50dm (lF2) 3 F 1, F 2 = 4 • 1 Hz 3 Η, F 1 = = 4 · 1 Hz 3 F 2, F 3 = 8 • 0 Hz 4 F 1, F 3 = 1 1.5 Hz 4 F 1, F 4 = 1 1 .5 Hz MR R 3 1 P, one millionth: This paper uses China National Standard (CNS) A4 Grid (210X 297mm) -20-(Please read the precautions on the back before filling out this page) " .. Order the printing of A7 _B7 _ by the Bayong Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs Ⅴ. Description of the invention (18) -147.37pdm J 1 p, f * = 928.0 Hz J 2 p, f * = 7 4. 5 Hz J 3 p, f »= 8.3 Hz J 3 p, f * = 11.4 Hz Example 4 Heptafluoroisopropyl Lithium pentacyanophosphate (VIII) Heptafluoroisopropyllithium pentafluorophosphate (VIII) is similar to Example 3 by reacting fluorophosphane (II d) with L i F in dimethoxyethane And get. As described above, the solution obtained after filtration can be used directly as an electrolyte solution, or the above-mentioned salt can be isolated by distilling off the solvent under high vacuum or crystallizing by adding hexane. The halothane mixture obtained in Example 1 can also be used to produce an electrolyte solution by reacting it with L i F without prior purification. The solution of the two lithium salts (VI I I) and (IX) obtained in this case can also be used as an electrolyte for a lithium battery. Both salts can be difficult in the same way as described above. Heptafluoroisopropyl lithium pentafluorophosphate (VIII) NMR 19F, part per million: (solvent: CD3COCD3; floor quasi-solvent: CC13F) -62 · 62dddsep (4 F 1) -73. I3p (IF2) Paper Standards applicable ® National Standard Rate (CNS) A4 Specification (210x297 mm) -21-1._Γ .----- a-- (Please read the note on the back before filling this page) Order A7 __B7_ 5 Description of the invention (19) -71.49pdd (6F4) — 183. 72dpsepm (IF3) J 2 f 1 · f 2 = 4 5. 4 Hz J 3 f 1 · f 3 = 3 · 6 Hz J 3 f 3 · f 4 = 4.2 Hertz J 4 Hertz NMR 31P, part per million: (solvent: CD3CN; external standard solution: 85% H a P Ο 4) -148. 16pddsep J 1 p, f1 = 841.0 Hz J 1 p , F2 = 717.0 Hz J 2 pf 3 = 6 8. 7 Hz J 3 p · f 4 = 4. 9 Hz 1,1,1,1,3,3,3-lithium hexafluoroisopropyl pentafluorophosphate (IX) Printed by the Shell Sample Consumer Cooperative of the Central Bureau of Standards and Quarantine of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) NMR 19F, part per million: (solvent: CD3COCD3: standard solvent: CC13F) -52.95dddsep (4F ' )-6 9. 0 4 p (IF2) -59. 40pdd (6F3) J 2 Hz J 3 F 1 H = 3 . 8 Hertz This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -22- Printed by the Consumer Sample Cooperative of the Central Samples Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (20) J 4 3 Hertz NMR 31P , Parts per million: (solvent: CDaCN; external standard solution: 85% Η 3 P 0 4) -145-82pddsep J 1 p · f 1 = 8 2 9 0 Hz J 1 p, f2 = 708.0 Hz J 2 p, h = 29.0 Hz, J 3 p, f3 = 12, .9 Hz. Cyclic experiments were performed using lithium heptafluoroisopropyl pentafluorophosphate (VIII), and the results shown in Figure 1 were obtained. These experiments were performed under the following conditions = potential interval: 0.0_3.0 volts; 3.0-6.0 volts change rate: 100 millivolts per second operating electrode: Pt, surface 稹 1 · 96 · 103 cubic Cm reference electrode: Li test electrode: Li electrochemical stability: up to 5.0 volt window Example 5 ginseng (pentacyanoethane) lithium tricyanophosphate (V) ginseng (pentafluoroethyl) three Lithium fluorophosphate (V) is similar to that of Example 3 by mixing the corresponding fluorophosphanes (V a) and L i F prepared in a manner similar to Example 2 in pre-dried dimethoxyethane. Derived from the reaction. (Please read the notes on the back before filling out this page) 7 ----------- Order — This paper size applies to China B house standard rate (CNS > A4 specification (210X297 mm)- 23- Printed by A7 __B7__ of the Central Bureau of Specimen Bureau of the Ministry of Economic Affairs __B7__ 5. Description of the Invention (21) In the case, the reaction solution obtained after the reaction and filtration can be used directly as the electrolyte solution, or a (v) can be used in皤 Drop off the solvent under vacuum or crystallize by adding hexane.》 Refer to (pentafluoroethyl) lithium trifluorophosphate (V) NMR 1 9 F, 1 part per million (· solvent ·· CD3C 〇CD3; Standard solvent: CC13F) -8 7.0 d (2 F 1) -43.6dm (lF2) -115.3m (4F3) -115.7m (2F5) -7 9 .7 m (3 F 6) -8 1.3 m (6 F 4) NMR 31P, part per million: (solvent: CD3CN: external standard solution: 85% Η 3 P Ο 4) -14 9.8 tdpt J 1 ρ, ρ · = 9〇2. 0 Hz. · J 1 p * f2 = 889.0 Hz J 2 p, f3 = 98.0 Hz J 2 p, f5 = 83.0 Hz DME reference (pentafluoroethyl) lithium trifluorophosphate complex (V) has a melting point 1 1 6 — 1 1 8 ° C and thermal stability up to 1 30 ° C. Figure 2 · · Using 1 liter of ginseng (pentafluoroethyl) lithium trifluorophosphate (v) This paper size applies to Chinese national standards (CNS > A4 size (210X297 mm) -24- If ----- ο-- ( Please read the notes on the back before filling in this f)-Order A7 B7_ V. Description of the invention P) Dissolve in DME with 10 ml LP 1 0 for the cycle experiment. The results of the first and fifth cycle operation experiments show In Figure 2. These experiments were performed under the following conditions: Potential interval: 0.0-3.0 volts; 3.0-6.0 volts change rate: 100 millivolts / second Operating electrode: Pt, surface area 1. 96 · 103 cubic centimeter reference electrode: Li test electrode: Li electrochemical stability: up to 5.0 volts. Brief description of the diagram. Figure 1. Cycle using lithium heptafluoroisopropyl pentafluorophosphate (VIII) Results obtained from experiments. Figure 2 shows the results obtained from cycling experiments using ginseng (pentafluoroethyl) trifluorophosphate (V). —; _ —; 1 ------ C heart -------- Order --------- line ο (Please read the notes on the back before filling out this page) The consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs Du printed this paper Of the applicable Chinese National Standard (CNS) A4 size (210 X 297 mm) -25-

Claims (1)

β ^ U8! Method Li Attachment 2 A: Patent Application No. 86114398 Chinese Amendment of Patent Scope Amendment in the Republic of China in September 88 Amendment • A method for the manufacture of a PFA (CHbFc (CF3) fluorolithium phosphate with the following general formula (I) ) d) e] '[I] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where a is 1. b is 0c is 0ci is 0e is 1 and the conditions are different, then b and c are not a) Alkane, chloromono-fluorodi-, fluorinated solvents with b) fluorinable products, c) aprotic poles, 2 or 1 3, 4 or 5 2 or 3, 2 or 3, and 2, 3 Or 4, if the ligands (C Η F total a + e equal to 6, b (CF 3) d) may be + c ten d total equal to 3 and 0 at the same time, the method is characterized by: -, Two-gas—or two-gas-one-chlorofluoroalkyl radical, chlorodione, chlorotrione or chlorotetraalkylphosphorane, fluoromono-, tri- or fluorotetraalkylphosphorane or trifluoromonohydroalkane Fluoride is fluorinated in an inert electrochemical fluorination method to separate the resulting product mixture into different ones by distillation and then fluorinated alkylphosphorane at -35 to 60 ° C in an isotropic solvent With fluorine Reaction with lithium. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) β ^ U8! Method Li Attachment 2 A: Patent Application No. 86114398 Chinese Amendment of Patent Scope Amendment in the Republic of China in September 88 Amendment • A method for the manufacture of a PFA (CHbFc (CF3) ) d) e] '[I] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where a is 1. b is 0c is 0ci is 0e is 1 and the conditions are different, then b and c are not a) Alkane, chloromono-fluorodi-, fluorinated solvents with b) fluorinable products, c) aprotic poles, 2 or 1 3, 4 or 5 2 or 3, 2 or 3, and 2, 3 Or 4, if the ligands (C Η F total a + e equal to 6, b (CF 3) d) may be + c ten d total equal to 3 and 0 at the same time, the method is characterized by: -, Two-gas—or two-gas-one-chlorofluoroalkyl radical, chlorodione, chlorotrione or chlorotetraalkylphosphorane, fluoromono-, tri- or fluorotetraalkylphosphorane or trifluoromonohydroalkane Fluoride is fluorinated in an inert electrochemical fluorination method to separate the resulting product mixture into different ones by distillation and then fluorinated alkylphosphorane at -35 to 60 ° C in an isotropic solvent With fluorine Reaction with lithium. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) 389742 Mi The Intellectual Property Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Co., Ltd. 2. The method according to item 1 of the scope of patent application, wherein the fluorination reaction is carried out at a temperature of -20 ° C to room temperature and normal pressure. 3. The method according to item 1 of the patent application range, wherein the distillation purification of the fluorinated reaction product is performed under an inert gas atmosphere. 4. The method according to item 1 of the patent application range, wherein the reaction with lithium fluoride is performed at room temperature. 5.-A compound having the following general formula (I a) [PFa (CHbFc (CFa) c) e) [la] wherein, as in the general formula (I), b is 0 or 1, c is 0, 1 , 2, or 3, d is 0, 1, 2, or 3 and e is 1, 2, 3, or 4, except that a is 1, 2, 3, or 4, which is defined in manufacturing as defined in item 1 of the scope of the patent application Intermediate products obtained from compounds of general formula (I). 6. — Lithium fluorophosphates with general formula (I) Li + [PFa (CHbFc (CFa) d) [I] where a is 1, 2, 3, 4 or 5, and b is 0 or 1 (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 * 297 mm) -2- 389742 A8 B8 C8 D8 VI. The scope of patent application C is 0 d Yes 0e is 1 1 1 2 2 or 3 2 or 3 3 or 4 and (CF 3) d) may be the total of b + c + d equal to the condition that if the ligands (CH b F are different, then a + The total number of e is equal to 63 and b and c are not at the same time. 7. If the lithium fluorophosphate of item 6 of the patent application scope is as follows: a) CF, FF CF, VCF-P-CF FF CF, ( Please read the notes on the back before filling in this page) U (II) b) CF, FF CF, CF—P-CH / / \ \ CF, FF CF3 U (in) c) Employees ’Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed d) CF 《F 、 / strict CH-P-CH // \ CF, FF CFS FwF C2 ^ ~ p-—c3f5 F C2F5 Lf LT This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -3- (IV) (V) 389742 VI. Application Patent scope e) A8 B8 C8 D8 f) F, / p CFr-P-CF, S / \ FFFF Λ / CFr-P-FV \ FFU LT (V!) (VII) • — — 111 ^ 1111111 IIIC (Please Read the notes on the back before filling this page) g) u (VUI) cf > Fn / p CF—PF 〇K / \ h) Cf 3 FX / p CH-P-F • / \ CF3 FFU (IX) . Line · Consumers' cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs. 8. If lithium fluorophosphate is applied for the scope of patent application No. 6 or 7, it can be used as a conductive salt in lithium batteries. 9. Lithium fluorophosphate as claimed in claim 6 or 7, which can be used as an electrolyte for lithium batteries. 10. If the lithium fluorophosphate of item 9 of the scope of patent application is used, it can be used as an electrolyte in a secondary lithium battery. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -4-