专利摘要:
PURPOSE: A borate salt, its preparation method, an electrolyte containing the borate salt, an electrochemical cell containing the electrolyte and a super condenser according to the electrochemical cell are provided to improve the electrochemical stability and the conductivity of an electrochemical cell. CONSTITUTION: The borate salt is represented by the formula M¬n+£BFx(CyF(2y+1-z)Hz)(4-x)|n ¬-, wherein 1<x<3; 1<=y<=8; 0<=z<=2y+1; and M is a monovalent, divalent or trivalent cation (1<=n<=3), is not K or Ba, and particularly is Li, NR1R2R3R4, PR5R6,R7R8, P(NR5R6)kR7mR8(4-k-m), C(NR5R6)(NR7R8)(NR9R10) or an aromatic heterocyclic cation(wherein k is 1-4, m is 0-3, k+m is 4 or less, R1 to R4 are CyF(2y+1-z)Hz, and R5 to R10 are H or CyF(2y+1-z)Hz). Preferably M is a N- and/or O- and/or S-containing aromatic heterocyclic cation.
公开号:KR20020062832A
申请号:KR1020020003834
申请日:2002-01-23
公开日:2002-07-31
发明作者:슈미트미카엘;퀴흐너안드레아스;프란츠클라우스-디어터;뢰센탈러게르드-볼커;비스키저만;콜로메이트세프알렉산더;카디로프알렉산더
申请人:메르크 파텐트 게엠베하;
IPC主号:
专利说明:

BORATE SALTS FOR USE IN ELECTROCHEMICAL CELLS
[2] The present invention relates to borate salts, their preparation methods and their use in electrochemical cells.
[3] Lithium ion batteries are the most promising systems for mobility applications. Areas of use range from high quality electronic devices (eg mobile phones, camcorders) to batteries for electrically driven cars.
[4] These batteries consist of a negative electrode, a positive electrode, a separator, and a nonaqueous electrolyte. The negative electrode is typically Li (MnMe z ) 2 O 4 , Li (CoMe z ) O 2 , Li (CoNi x Me z ) O 2 or other lithium insert and insertion compound. The anode may consist of lithium metal, soft and hard carbon, graphite, graphitic carbon or other lithium inserts and intercalation compounds or alloying compounds. Examples of the electrolyte include lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 or LiC (CF 3 SO 2 ) 3 and aprotic Mixtures thereof are used in the solvent.
[5] Conventional lithium conductive salts exhibit various disadvantages. Some conductive salts (eg LiBF 4 ) have low cycle yields. Other conductive salts (eg LiPF 6 ) have low thermal stability and other conductive salts (eg LiAsF 6 ) are not particularly suitable because of their toxicity and low environmental friendliness.
[6] LiBF 4 has higher thermal stability than LiPF 6 . However, this forms an electrolyte with very low conductivity in an aprotic solvent and therefore is not very suitable for high-energy batteries.
[7] To avoid these drawbacks, other lithium salts have been proposed.
[8] For example, imides, bis (trifluoromethylsulfonyl) imide according to US Pat. No. 45054997, and metaides, in particular tris (trifluoromethylsulfonyl) methide according to US Pat. No. 5273840. Has been proposed. These salts have high anodic stability and can form solutions with high conductivity in organic aprotic solvents.
[9] However, aluminum, which is generally used as a cathode current collector, is not surface stabilized to an appropriate degree, at least by imides (La Dominey, Current State of Art on Lithium Battery Electrolyte, edited by G. Pistoia, Lithium Batteries). , Amsterdam, Elsevier, 1994].
[10] In contrast, the preparation and purification of menatine is very costly. In addition, the electrochemical properties, for example oxidative stability and surface stabilization of aluminum, depend very much on the purity of the metanide (WO 99/07676).
[11] As another alternative, EP 0698301 proposes lithium spiroborate and Electrochemical and Solid State Letters, 2 (2) 60-62 (1999), propose lithium spirophosphate. Because of the use of bivalent ligands, these salts have very high thermal decomposition points in some cases of over 200 ° C. However, since it has an oxidation potential of 4.3 V at best for Li / Li + , it has a highly oxidizable electrode material, for example LiMn 2 O 4 or LiCo 1-x Ni x O 2 (0 <x <1). Oxidation stability is not suitable for use in lithium batteries.
[12] EP 929558 discloses the use of lithium fluoroalkylphosphates, preferably lithium fluoroalkylphosphates with perfluorinated ethyl or isopropyl groups. The thermal stability and hydrolysis resistance of these lithium salts were greatly increased compared to LiPF 6 .
[13] It is an object of the present invention to provide salts for electrolytes for use in electrochemical cells which are electrochemically stable and have high conductivity.
[1] 1 shows the first half cycle of the voltamogrammes of each cycle.
[14] The object of the present invention is obtained by the borate salt of formula (I):
[15] M n + [BF x (C y F 2y + 1-z H z) 4-x] n -
[16] Where
[17] 1 <x <3
[18] 1≤y≤8,
[19] 0 ≦ z ≦ 2y + 1,
[20] M is a monovalent to trivalent cation (1 ≦ n ≦ 3), not potassium and barium, in particular Li, NR 1 R 2 R 3 R 4 , PR 5 R 6 R 7 R 8 , P (NR 5 R 6 ) k R 7 m R 8 4-km , C (NR 5 R 6 ) (NR 7 R 8 ) (NR 9 R 10 ) or aromatic heterocyclic cations, especially nitrogen- and / or oxygen- and / or sulfur -Containing aromatic heterocyclic cations,
[21] Wherein k is 1 to 4, m is 0 to 3, k + m is 4 or less, R 1 to R 4 are C y F 2y + 1-z H z , and R 5 to R 10 are H or C y F 2y + 1-z H z
[22] The present invention relates to methods of preparing these compounds and their use as electrolytes for electrochemical cells, batteries, double layer capacitors and supercapacitors.
[23] Because of the asymmetrical structure of the anion, the solubility of the salts of the present invention in aprotic solvents is significantly higher than the solubility of LiBF 4 , Li [BF 3 (CF 3 )] and Li [BF 3 (CH 3 )], for example For example, solubility in pure diethylene carbonate was found to be significantly higher than 2.5 mol / l.
[24] Surprisingly, the salts of the present invention have been found to have significantly higher conductivity compared to LiBF 4 in typical solvent mixtures for electrochemical cells, for example EC / DEC. For Li [BF 3 (CF 3 )] in EC / DEC, the conductivity value was found to be similar to that of LiPF 6 .
[25] Salts have been found to have very good hydrolytic stability. Thus, for example, the synthesis of Li [BF 3 (CF 3 )] from an aqueous medium has been successful.
[26] In addition, the salts of the present invention exhibit an electrochemical stability comparable to that of LiPF 6 .
[27] Thus, the borate salts prepared according to the invention are particularly suitable for use in electrochemical cells. Borate salts can be used with other lithium salts or alternatively with borate complexes in electrolytes for secondary lithium batteries.
[28] Borate salts can also be used in electrolytes including conventional conductive salts. Examples of suitable electrolytes include conductive salts selected from the group consisting of LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 and LiC (CF 3 SO 2 ) 3 and mixtures thereof. It's things to include. The electrolyte may also include organic isocyanates to reduce the water content (DE 199 44 603). The electrolyte may also comprise organic alkali metal salts as additives (DE 199 10 968). Alkali metal borate of Formula 2 is suitable:
[29] Li + B - (OR 1) m (OR 2) p
[30] Where
[31] m and p are 0, 1, 2, 3 or 4, where m + p is 4,
[32] R 1 and R 2 are the same or different and are optionally bonded directly to each other via a single or double bond and are each, individually or together, an aromatic or aliphatic carboxylic acid, dicarboxylic acid or sulfonic acid radical, or
[33] Each independently or together, an aromatic ring selected from the group consisting of phenyl, naphthyl, anthracenyl and phenanthrenyl, unsubstituted 1 to 4 with A or Hal, or
[34] Each independently or together, a heterocyclic aromatic ring selected from the group consisting of unsubstituted pyridyl, pyrazyl and bipyridyl 1-3 substituted with A or Hal, or
[35] Each independently or together, an aromatic hydroxy acid selected from the group consisting of aromatic hydroxycarboxylic acid and aromatic hydroxysulfonic acid, unsubstituted 1 to 4 or substituted with A or Hal,
[36] Hal is F, Cl or Br,
[37] A is alkyl having 1 to 6 carbons which may be substituted 1 to 3 with halogen.
[38] Also suitable are alkali metal alkoxides of formula (3):
[39] Li + OR -
[40] Where
[41] R is an aromatic or aliphatic carboxylic acid, dicarboxylic acid or sulfonic acid radical, or
[42] 1 to 4 substituted by A or Hal, or an aromatic ring selected from the group consisting of unsubstituted phenyl, naphthyl, anthracenyl and phenanthrenyl, or
[43] 1 to 3 substituted by A or Hal, or a heterocyclic aromatic ring selected from the group consisting of unsubstituted pyridyl, pyrazyl and bipyridyl, or
[44] An aromatic hydroxy acid selected from the group consisting of aromatic hydroxycarboxylic acid and aromatic hydroxysulfonic acid, unsubstituted or substituted with 1 to 4 with A or Hal,
[45] Hal is F, Cl or Br,
[46] A is alkyl having 1 to 6 carbons which may be substituted 1 to 3 with halogen.
[47] The electrolyte may also comprise a compound of formula 4 (DE 199 41 566):
[48] [([R 1 (CR 2 R 3) k] 1 A x) y Kt] + - N (CF 3) 2
[49] Where
[50] Kt is N, P, As, Sb, S or Se,
[51] A is N, P, P (O), O, S, S (O), SO 2 , As, As (O), Sb or Sb (O),
[52] R 1 , R 2 and R 3 are the same or different and are H, halogen, substituted and / or unsubstituted alkyl, C n H 2n + 1 , substituted and / or unsubstituted, having 1 to 18 carbon atoms and one or more Alkenyl having a double bond, substituted and / or unsubstituted, alkynyl having 1 to 18 carbon atoms and having at least one triple bond, substituted and / or unsubstituted cycloalkyl C m H 2m-1 , unsubstituted /, 1 or multiple substituted phenyl, or substituted and / or unsubstituted heteroaryl,
[53] A may be included in R 1 , R 2 and / or R 3 at various positions,
[54] Kt may be included in a cyclic or heterocyclic ring,
[55] The groups bonded to Kt are the same or different,
[56] At this time,
[57] n is 1 to 18,
[58] m is 3 to 7,
[59] k is 0 or 1 to 6,
[60] l is 1 or 2 when x is 1, 1 when x is 0,
[61] x is 0 or 1,
[62] y is 1 to 4.
[63] The process for preparing these compounds is characterized by reacting an alkali metal salt of formula (5) with a salt of formula (6) in a polar organic solvent:
[64] D + - N (CF 3) 2
[65] [([R 1 (CR 2 R 3) k] 1 A x) y Kt] + - E
[66] Where
[67] D + is selected from the group consisting of alkali metals,
[68] Kt, A, R 1 , R 2 , R 3 , k, l, x and y are as defined in the compound of Formula 4,
[69] E - is F -, Cl -, Br - , I -, BF 4 -, ClO 4 -, AsF 6 -, SbF 6 - or PF 6 - is.
[70] However, compounds of formula (7) (DE 199 53 638) prepared by reacting partially or perfluorinated alkyl sulfonyl fluoride with dimethylamine in an organic solvent, and the corresponding boron or in Lewis acid / solvent addition It is also possible to use an electrolyte comprising a complex salt of formula 8 (DE 199 51 804) prepared by reacting water with lithium or tetraalkylammonium imide, metaide or triflate:
[71] X- (CYZ) m -SO 2 N (CR 1 R 2 R 3 ) 2
[72] [Wherein,
[73] X is H, F, Cl, C n H 2n + 1 , C n F 2n-1 or (SO 2 ) k N (CR 1 R 2 R 3 ) 2 ,
[74] Y is H, F or Cl,
[75] Z is H, F or Cl,
[76] R 1 , R 2 and R 3 are H and / or alkyl, fluoroalkyl or cycloalkyl,
[77] m is 0 to 9, and when X is H, m is not 0,
[78] n is 1 to 9,
[79] k is 0 when m is 0 and 1 when m is 1-9.]
[80] M x + [EZ] y- x / y
[81] [Wherein,
[82] x and y are 1, 2, 3, 4, 5 or 6,
[83] M x + is a metal ion,
[84] E consists of BR 1 R 2 R 3 , AlR 1 R 2 R 3 , PR 1 R 2 R 3 R 4 R 5 , AsR 1 R 2 R 3 R 4 R 5 and VR 1 R 2 R 3 R 4 R 5 Lewis is chosen from the group,
[85] Wherein R 1 to R 5 are the same or different and are optionally bonded directly to each other by a single bond or a double bond, and each independently or together halogen (F, Cl or Br); C 1 -C 8 alkyl or alkoxy radicals which may be partially or fully substituted with F, Cl or Br; Aromatic rings, optionally linked via oxygen, selected from the group consisting of phenyl, naphthyl, anthracenyl and phenanthrenyl, unsubstituted or substituted with 1 to 6 carbon atoms, C 1 -C 8 alkyl, or F, Cl or Br ; Or C 1 -C 8 alkyl, or heterocyclic aromatic ring, optionally substituted via oxygen, selected from the group consisting of 1 to 4 substituted with F, Cl or Br, or unsubstituted pyridyl, pyrazyl and pyrimidyl ego,
[86] Z is OR 6 , NR 6 R 7 , CR 6 R 7 R 8 , OSO 2 R 6 , N (SO 2 R 6 ) (SO 2 R 7 ), C (SO 2 R 6 ) (SO 2 R 7 ) ( SO 2 R 8 ) or OCOR 6, wherein R 6 to R 8 are the same or different and are optionally bonded directly to each other by a single bond or a double bond, each independently or together with hydrogen or R 1 to R 5 As defined in.
[87] Borate salts of formula 9 (DE 199 59 722) may also be present.
[88]
[89] Where
[90] M is a metal ion or a tetraalkylammonium ion,
[91] x and y are 1, 2, 3, 4, 5 or 6,
[92] R 1 to R 4 are the same or different and are C 1 -C 8 alkoxy or carboxyl radicals, optionally directly bonded to each other by a single bond or a double bond.
[93] These borate salts are prepared by reacting a 1: 1 mixture of lithium alkoxide and borate or lithium tetraalkoxyborate with a suitable hydroxyl or carboxyl compound in a ratio of 2: 1 to 4: 1 in an aprotic solvent.
[94] The additive may also be used in an electrolyte comprising lithium fluoroalkylphosphate of formula 10, except for the compound of formula 11:
[95] Li + [PF x (C y F 2y + 1-z H z ) 6-x ] -
[96] Li + [PF a (CH b F c (CF 3 ) d ) e ] -
[97] Where
[98] 1≤x≤5,
[99] 3≤y≤8,
[100] 0 ≦ z ≦ 2y + 1,
[101] The ligands (C y F 2y + 1-z H z ) are the same or different,
[102] a is an integer from 2 to 5,
[103] b is 0 or 1,
[104] c is 0 or 1,
[105] d is 2,
[106] e is an integer from 1 to 4,
[107] Provided that b and c are each non-zero at the same time,
[108] the sum of a + e is 6,
[109] The ligands (CH b F c (CF 3 ) d ) are the same or different (DE 100 089 55).
[110] Method for preparing a lithium fluoroalkyl phosphate of Formula 10 is a general formula H m P (C n H 2 n + 1 ) 3-m , OP (C n H 2n + 1 ) 3 , Cl m P (C n H 2n + 1 ) 3-m , F m P (C n H 2n + 1 ) 3-m , Cl o P (C n H 2n + 1 ) 5-o , F o P (C n H 2n + 1 ) 5-o At least one of the compounds of is fluorinated by electrolysis in hydrogen fluoride, the resulting mixture of fluorinated products are separated by extraction, phase separation and / or distillation, and the resulting fluorinated alkyl-phosphorane Excluded and reacted with lithium fluoride in the aprotic solvent mixture, and the resulting salt of formula 10 is purified and isolated in a conventional manner.
[111] Additives can be used in electrolytes for electrochemical cells containing a positive electrode material consisting of a coated metal core selected from the group consisting of Sb, Bi, Cd, In, Pb, Ga and tin or alloys thereof (DE 100 16 204 number). The process for preparing the positive electrode material comprises: a) preparing a suspension or sol of a metal or alloy core in eutropin, b) emulsifying the suspension with C 5 -C 12 hydrocarbons, c) emulsifying the emulsion with a metal or alloy core Precipitated in and d) heating the system to convert the metal hydroxide or oxyhydroxide to the corresponding oxide.
[112] Additives can also be used in electrolytes for electrochemical cells having a negative electrode made of conventional lithium inserts and insertion compounds, but also suspending the particles in an organic solvent, and a solution of a hydrolyzable metal compound and a hydrolysis solution. It can also be used in the case of a negative electrode material (DE 199 22 522) consisting of lithium mixed oxide particles coated with one or more metal oxides by addition to the suspension, followed by filtration, drying and optionally calcining the coated particles. have. They may also consist of lithium mixed oxide particles coated with one or more polymers obtained by the process of suspending the particles in a solvent, subsequently filtering the coated particles, drying and optionally calcining. DE 199 46 066). The additives of the present invention can likewise be used in systems having a negative electrode consisting of lithium mixed oxide particles with at least one coating of an alkali metal compound and a metal oxide (DE 100 14 884). Methods of making these materials include suspending particles in an organic solvent, adding alkali metal compounds suspended in an organic solvent, adding a metal oxide dissolved in an organic solvent, adding a hydrolysis solution to the suspension, and applying the coated particles. Subsequently filtered, dried and calcined.
[113] General examples of the invention are described in more detail below.
[114] The BF 3 / solvent complex is reacted 1: 1 with alkyllithium at a temperature below 0 ° C. The mixture is allowed to warm slowly to room temperature. After some of the solvent is removed, the solids are filtered off. The solid is purified in a conventional manner.
[115] Further processes for preparing the salts of the present invention start with lithium salts, which are described in Chambers, J. Am. . Soc, known 82, 5298 (1960)] [ B (CF 3) F 3] - salt in a 1: is reacted with 1. The mixture is stirred at elevated temperature and then filtered. Aprotic, non-aqueous solvents, preferably solvents used in electrochemical cells, are added to the reaction mixture and the mixture is dried.
[116] Borate salts of the invention are also described in Chambers, J. Am. . Soc, 82, 5298] known [B (CF 3) F 3 ] in - the salt and the lithium salt is from 1: 1 to 1: 1.5 is reacted, it can be obtained by stirring the mixture in water at elevated temperatures. The reaction mixture is heated at the boiling point for 0.5 to 2 hours, the water is removed, a suitable solvent, preferably the solvent used in the electrochemical cell, is subsequently added and the mixture is dried.
[117] The following examples are intended to illustrate the invention in more detail, and are not intended to be limiting.
[118] Example
[119] Example 1:
[120] Lithium methyltrifluoroborate
[121] 3.1 g of 5% diethyl ether solution of MeLi (7.1 mmol of MeLi) was slowly added dropwise to 1.0 g (7.1 mmol) of boron trifluoride etherate in 5 ml of diethyl ether at −10 ° C., followed by reaction mixture Warmed to room temperature with stirring for 2 h. Half of the solvent was removed and the white solid was filtered off and washed with 1 ml of ether. The ether residue was removed under reduced pressure. Yield: 0.5 g (85%). ( 19 F NMR: -154.7 (m); 1 H NMR: -1.48 (s)).
[122]
[123] Example 2:
[124] Lithium trifluoromethyltrifluoroborate
[125] 21.27 g (0.071 mole) of trimethylstannonium trifluoromethyltrifluoroborate was added to 1.84 g (0.071 mole) of lithium fluoride in 100 ml of water. The mixture was stirred at 60 ° C. for 12 h and then the insoluble trimethylfluorostanna was filtered off, 80% of the water was removed and the trimethylfluorostanza residue was filtered off (10.2 g of Li + [B (CF 3 ) F 3 ). - it was expected). The water was then pumped out until the solution became viscous.
[126]
[127] The viscous, water-containing reaction mixture (contaminated with 15% LiBF 4 ) is dissolved in 50 ml of diethyl carbonate, dried using magnesium sulfate, filtered, 100 ml of CCl 4 is added and the mixture is Stirred. Precipitated LiBF 4 was filtered and the solution was monitored for BF 4 using a 19 F-NMR spectrometer. The salt content was confirmed using a volatile reference containing CF (CF 3 -cyclo-C 6 H 11 ), and all CCl 4 was removed under reduced pressure (15 mmHg). Diethyl carbonate was removed, with CCl 4 supplemented. Diethyl carbonate was then further pumped off to adjust the solution to the desired concentration.
[128] 19 F-NMR: −76.0 (q, 3 J BF = 33.6 Hz); -156.0 (q, 1 J BF = 40.7 Hz). Data on negative ions correspond to those for reference [1,2].
[129] Example 3:
[130] Tetraethylammonium Trifluoromethyltrifluoroborate
[131] Lithium trifluoromethyltrifluoroborate was reacted with tetraethylammonium chloride in acetonitrile at room temperature to produce tetraethylammonium trifluoromethyltrifluoroborate. The lithium chloride formed was filtered off and the product was recrystallized from acetonitrile / methyl tert-butyl ether.
[132] 19 F-NMR data for the anion corresponded to that of Example 2.
[133] Example 4:
[134] Tetraethylphosphonium trifluoromethyltrifluoroborate
[135] Lithium trifluoromethyltrifluoroborate was reacted with tetraethylphosphonium chloride in acetonitrile at room temperature to produce tetraethylphosphonium trifluoromethyltrifluoroborate. The lithium chloride formed was filtered off and the product was recrystallized from acetonitrile / methyl tert-butyl ether.
[136] 19 F-NMR data for the anion corresponded to that of Example 2.
[137] Example 5:
[138] Preparation via Bu 3 Sn [BF 3 CF 3 ]
[139] 3.2 mmol (0.22 g) of boron trifluoride were condensed at -196 ° C. with 1.1 g (3.1 mmol) trifluoromethyltri-n-butylstanane and 4 ml of carbon tetrachloride. The mixture was allowed to warm to room temperature over 10 minutes. After removal of the solvent by pumping, so that the adult 1.3g Bu 3 Sn + [BF 3 CF 3] - the left.
[140] Example 6:
[141] Bu 3 Sn + [BF 3 CF 3] - borate and methyl trifluoroacetate as lithium trifluoroacetate from LiF
[142] 1.3 g (3.1 mmol) Bu3Sn+[BF3CF3]-, 0.08 g (3.1 mmol) of LiF and 30 ml of hot water were introduced into a round bottom flask with a magnetic stirrer. The mixture was stirred for 12 hours and then heated to boiling for 1 hour. Precipitated fluorotributylstannan was filtered off. Water was removed from the remaining solution until the solution became viscous. Li+[B (CF3) F3]-See above for further isolation.
[143] 19 F-NMR data for the anion corresponded to that of Example 2.
[144] 19 F-NMR [2]: −76.0 (q, 3 J BF = 33.6 Hz); -156.0 (q, 1 J BF = 40.7 Hz). Data on negative ions correspond to those for reference [1,2].
[145] Example 7:
[146] Lithium bis (trifluoromethyl) difluoroborate
[147] The hot water of 600ml of 78.0g (182.7mmol) Bu 3 Sn + [ BF 3 CF 3] - is added to the LiF and 7.1g (274.1mmol) and the mixture heated to boiling for an hour and then stirred for 12 hours It was. The precipitated fluorotributylstannan was filtered off and water was removed until the solution became viscous.
[148] Then 150 ml of diethyl carbonate was added to the viscous solution. Water was removed from the solution at a high degree of vacuum (in this case diethyl carbonate is better coordinated with lithium than with water, which is why water can be removed first). Li + BF 4 -, Li + [BF 3 CF 3] -, Li + [BF 2 (CF 3) 2] - and the mixture of was obtained. The solution was extracted several times with 4 × 30 ml of water and 19 F-NMR spectrometer confirmed that (Li + BF 4 and Li + [BF 3 CF 3 ] ) were present in the aqueous phase. The diethyl carbonate solution was dried using magnesium sulfate, filtered and 0.2 g of lithium carbonate was added (to neutralize the existing HF) and the mixture was filtered again (LiCO 3 and LiF were essentially di Insoluble in ethyl carbonate). PH was checked using indicator paper. 1,1-bis (trifluoromethyl) perfluorocyclohexane (boiling point: 120 ℃) was added to check the salt content. In the last step, 1,1-bis (trifluoromethyl) perfluorocyclohexane was removed from the solution under high vacuum. This yields a solution of 6.7 g of lithium bis (trifluoromethyl) difluoroborate in 22.8 g of diethyl carbonate.
[149] 19 F-NMR data for the anion correspond to that of [2].
[150] Example 8:
[151] Tetraethylammonium bis (trifluoromethyl) difluoroborate
[152] Lithium bis (trifluoromethyl) difluoroborate was reacted with tetraethylammonium chloride in acetonitrile at room temperature to produce tetraethylammonium bis (trifluoromethyl) difluoroborate. The lithium chloride formed was filtered off and the product was recrystallized from acetonitrile / methyl tert-butyl ether.
[153] 19 F-NMR data for the anion correspond to that of [2].
[154] Example 9:
[155] Conductivity research
[156] Concentration [mol / dm 3 ]Conductivity [mS / cm]Li [BF 3 CF 3 ]Li [BF 2 (CF 3 ) 2 ]Li [BF 3 (CH 3 )]LiBF 4 LiPF 40.55.9 6.4 0.756.57.23.3 One6.1 3.43.17.0 1.255.4 3.3 6.4
[157] Example 10:
[158] Electrochemical stability
[159] In a measurement cell having a platinum working electrode, a lithium reverse electrode and a lithium reference electrode, three cycles of voltammograms were recorded one by one. To this end, the potential was first increased from a resting potential to 6.0 V for Li / Li + at a feed rate of 10 mV / s and then returned to the resting potential for further processing.
[160] The electrolyte used was a 0.5 molar Li [BF 3 CH 3 ] and Li [BF 3 CF 3 ] solution in EC / DEC (50:50 wt.%).
[161] According to the present invention there is provided a salt for an electrolyte for use in an electrochemical cell which is electrochemically stable and has high conductivity.
权利要求:
Claims (7)
[1" claim-type="Currently amended] Borate salt of Formula 1:
Formula 1
M n + [BF x (C y F 2y + 1-z H z) 4-x] n -
Where
1 <x <3
1≤y≤8,
0 ≦ z ≦ 2y + 1,
M is a monovalent to trivalent cation (1 ≦ n ≦ 3), not potassium and barium, in particular Li, NR 1 R 2 R 3 R 4 , PR 5 R 6 R 7 R 8 , P (NR 5 R 6 ) k R 7 m R 8 4-km , C (NR 5 R 6 ) (NR 7 R 8 ) (NR 9 R 10 ) or aromatic heterocyclic cations, especially nitrogen- and / or oxygen- and / or sulfur -Containing aromatic heterocyclic cations,
Wherein k is 1 to 4, m is 0 to 3, k + m is 4 or less, R 1 to R 4 are C y F 2y + 1-z H z , and R 5 to R 10 are H or C y F 2y + 1-z H z .
[2" claim-type="Currently amended] a) react with alkyllithium at 1: 1 with cooling the BF 3 / solvent complex, remove most of the solvent after slow warming, subsequently filter the solids, wash with a suitable solvent, or
b) reacting the lithium salt with the B (CF 3 ) F 3 salt 1: 1 in a suitable solvent, the mixture is stirred at elevated temperature, the solvent is removed, and an aprotic, non-aqueous solvent, preferably an electrochemical cell Add the solvent used in the reaction mixture and dry the mixture, or
c) reacting the B (CF 3 ) F 3 salt with lithium salt in water at an elevated temperature of 1: 1 to 1: 1.5, heating the mixture at boiling point for 0.5 to 2 hours, removing water, aprotic, A non-aqueous solvent, preferably a solvent used in an electrochemical cell, is added to the reaction mixture and the mixture is dried.
[3" claim-type="Currently amended] An electrolyte comprising at least one compound of claim 1.
[4" claim-type="Currently amended] The method of claim 3, wherein
An electrolyte comprising one or more other conductive salts or additives.
[5" claim-type="Currently amended] An electrochemical cell containing the electrolyte of claim 3 or 4.
[6" claim-type="Currently amended] Battery, double layer capacitor or supercapacitor according to claim 5.
[7" claim-type="Currently amended] Use of the borate salt of claim 1 for the preparation of an electrolyte for an electrochemical cell, battery, double layer capacitor or supercapacitor.
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同族专利:
公开号 | 公开日
TW531925B|2003-05-11|
CA2368990A1|2002-07-24|
EP1229038A1|2002-08-07|
JP2002305024A|2002-10-18|
DE10103189A1|2002-07-25|
RU2002101503A|2003-09-20|
CN1367174A|2002-09-04|
BR0200169A|2002-10-15|
US20020160261A1|2002-10-31|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题
法律状态:
2001-01-24|Priority to DE2001103189
2001-01-24|Priority to DE10103189.0
2002-01-23|Application filed by 메르크 파텐트 게엠베하
2002-07-31|Publication of KR20020062832A
优先权:
申请号 | 申请日 | 专利标题
DE2001103189|DE10103189A1|2001-01-24|2001-01-24|New alkyl group-containing borate saltsfor use in e.g. batteries, have an asymmetrical anion structure|
DE10103189.0|2001-01-24|
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