CA1046237A - Method for lithiating metal chalcogenides and intercalated products thereof - Google Patents
Method for lithiating metal chalcogenides and intercalated products thereofInfo
- Publication number
- CA1046237A CA1046237A CA226,256A CA226256A CA1046237A CA 1046237 A CA1046237 A CA 1046237A CA 226256 A CA226256 A CA 226256A CA 1046237 A CA1046237 A CA 1046237A
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- Prior art keywords
- lithium
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- metal chalcogenide
- chalcogenide
- metal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/12—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE Metal chalcogenides having the general formula MZy wherein Z is S, Se and Te; M is an element from Group IVB, VB, Mo, W, Tc, Pt, Re, Ge, Sn and Pb and y is 1.0 to 4.0 are lithiated by lithium compounds selected from LiR1, LiC(R1)3, LiN(R1)2, LiBH(R1)3, LiR1?R2 and LiAlH4?R2 wherein R1 is a hydrocarbon radical of 1 to 8 carbon atoms and R2 is a chelating polyamine.
Description
1 04~ Z 3 7 1 The present invention is directed toward ~ novel
2 method of lithiating compounds of metal chalcogenides which
3 exist in relatively well ordered crystal structures having a
4 plurality of planes with relatively weak attractive forces between the planes, and the novel lithium intercalated pro-6 ducts thereof 7 Because of the relatively weak forces between the 8 pLanes of metal chalcogenides, it has been found possible to 9 introduce a wide variety of molecules between the planes to form products which are stable at ambient temperatures but 11 which will lose the molecules between the planes under appro-l2 priate conditions, ~hese intercalated products ha~e shown 13 many desirable properties including superconductivity and 14 lubricating properties.
Various methods are known for the preparation of l6 lithium in~rcalated metal chalcogenides, for example, see the 17 followlng: Journal of Chemical Ph~sics, Volume 58, page 697 18 et seq (1973); published German patent application 2,061,162;
19 National Bureau of Standards Special Publication No, 364;
pages 625 et seq (1972); Journal of Les~ Common Metal~, 21 Vslume 20, page 121 et seq (1970); Science, Volume 175, page 22 884 et seq (1972); C.R. Acad. SC. Paris, 5., 276, Series C, 23 page 1283 et seq (1973).
24 Basically, each of the foregoing references dis-closes preparative techniques that require extreme conditions 26 or relatively sophisticated or complicated handling; and, 27 each of the techniques often fail to yield suitable products.
28 For example, insertion of lithium in the metal dichalcogen-29 ides by the foregoing techniques typically results in less than 0~7 moles of lithium being inserted in the metal dichal-31 cogenide Often multiphase products result which include un-32 wanted molecules, such as ammonia or nitrogenous contaminants, - 2 _ ~
104~3'7 1 being inserted within the planes of the transition metal 2 chalcogenide.
3According to the present invention there is pro-4 vided a method of lithiating metal chalcogenides under con-trolled conditions. In its simplest sense, the method of 6 the instant invention compr~ses adding a specific lithium 7 compound to a transition metal chalcogenide. The specific 8 lithium compound i8 selected from the group con isting of 9LiRl, LiC(Rl)3, LiN(Rl)2~ L~BH(Rl)3, LiRl-R2 and LiALH4-R2 lo wherein Rl is a hydrocarbon radical havlng from l to 8 11 carbon atoms and R2 is a chelating polyam~ne~ Typical hy-12 drocarbon radicals lnclude vinyl, butyl, phenyl, methyl and 13 ethyl radicalsO Preferred chelating polyamine~ include tetramethylethylene diamine and pentamethyldiethylene tri-amine. The metal chalcogenide to which the reactive lith-16 ium compound is added has the general formula MZy wherein Z
17 is an element selected from the group consisting of sulfur, 18 selenium and tellurium; y i8 a number between l.0 and 4O0 19 and M is an element selected from the group consisting of Group IVB elements, Group VB elements, molybdenum, tungsten, 21 technetium, pLatinum, rhenium, germanium, tin and lead but 22 not vanadium when Z is sulfur and y is 2. Preferably, M
23 in the formula MZy is titanlum or tantalum (e~pecially ti-24 tanium); Z is preferably sulfur or selenium (especially pre-ferred is sulfur), and3 y preferably has a numerical value 26between abo~t 1.60 and about 2.02, especlally 2Ø
27In another aspect of the present invention, there 28 is provided novel lithium intercalated metal chalcogenides 29 having the general formula LixMZy wherein Z is sulfur and selenium; M i~ an element selected from Group VB elements, 31 hafnium and zirconium but not vanadium when Z is sulfur; y 32is a numerical value between 1.67 and 2.02 and x is a numer-104~Z3'7 l ical value between 0.8 and 1.2 and preferably 009 to l~lo 2 In yet another aspect of the present invention 3 there is prov~ded a nitrogen-free lithium titanium sulfide 4 of the formula LiXTiSy where x is a numerical value from 0.8 to 1.2; and preferably 0.9 to 1.1 and y is a numerical 6 value from 1~67 to 2.02.
7 In the practice of the present inventlon metal 8 chalcogenide~ are lithiated under controlled conditions by 9 adding a specific lithium compound to a met~l chalcogenide The lithium compound employed i8 selec~ed from the group 11 consisting of LiRl, LiC(Rl)3, LiN~R1~2, LiRloR2 and l2 LiALH4-R2 wherein Rl is a hydrocarbon radical having from 3 1 to 8 carbon atoms and R2 is a chelating polyamine~ Typi-14 cal hydrocarbon radicals include vinyl, butyl,phenyl, methyl, ethyl and the like. Typical chelating polyamines include l6 tetramethylethylene di~mine, pentamethyldiethylene triamine 17 and hexamethyltriethylene tetramine. In the preferred em-18 bodiment of the present invention3 the lithium compound is 19 n-butyl lithium.
The foregoing l~thium compounds are prepared by 21 wel~knor~n techniques which form no part of the present in-22 vention. Indeed, the preferred lithium compound, as well 23 as others, is a commercially available compound.
24 In general, the lithium compound is dissolved in an aprotic solvent or diluent such as hexane, heptane, ben-26 zene, toluene or tetrahydrofuran. Then, the solution of the -27 lithium compound is added to the metal chalcogenide, at a 28 temperature in the range of from about -100S. to 100C., 29 and preferably at ambient tempera~ures~ The mixture is al-lowed to stand (stirring is optional) for a time sufficient 31 for lithiation of the metal chalcogenide to occur. Generally, 32 such reaction time i8 between a half day to 30 days or more.
-104~Z37 1 While stirring tends to speed the lithiation of the metal 2 chalcogenide, stirring also tends to promote the formation 3 of powdered productsO Thus, if the crystal size of metal 4 chalcogenide is to be substantially maintained stirring the mixture i8 not preferred~
6 As will be appreciated the specific lithium com-7 pounds are generally air or moisture sensitive and conse~
8 quently the lithium compound and the metal chalcogenide are 9 handled in inert gas atmo~pheres, such as nitrogen, helium o or argon.
1 Although a stoichiometric amount of the lithium 12 compound and metal chalcogenide can be used, it is preferred in the practice of the pre~ent invention to use an excess of the specific lithium compound~ For example~ it is particu-larly preferred to use a 50% mole excei~ of the lithium 16 compound.
17 The reaction can be followed by assaying a ~uper-8 natant liquid for basic lithium or in the case of when n 19 butyl lithium is employed as the lithium compound, the ex-tent of reaction also can be followed by monitor~ng the re-21 action mixture for the formation of octane, a coproduct.
22 Generally, the reaction i8 carried out at atmos-23 pheric pressure, although pressures up to 5 atmospheres or 24 more may be employed.
As indic~ted previously, the metal chalcogenide 26 employed in the pre~ent invention ha~ the general formula 27 MZy wherein M is an element selected from the group consist-28 ing of Group IYB elements, Group VB elements, molybdenum, 29 tungsten, technetium, platinum, rhenium, germanium, tin and lead, Z i~ a chalcogen, i.e. Z is an element selected from 31 the group consisting of sulfur, selenium and tellurium; and 32 y has a numerical value between l.0 and about 4.0; provided, ~ 5 -lO~t~Z37 1 however, that when M i8 vanadium and y is 2, Z is selenium 2 and tellurium onlyO
3 The term "Group" refers to the particular Group 4 of the Pericdic Table of the Elements of the type set forth
Various methods are known for the preparation of l6 lithium in~rcalated metal chalcogenides, for example, see the 17 followlng: Journal of Chemical Ph~sics, Volume 58, page 697 18 et seq (1973); published German patent application 2,061,162;
19 National Bureau of Standards Special Publication No, 364;
pages 625 et seq (1972); Journal of Les~ Common Metal~, 21 Vslume 20, page 121 et seq (1970); Science, Volume 175, page 22 884 et seq (1972); C.R. Acad. SC. Paris, 5., 276, Series C, 23 page 1283 et seq (1973).
24 Basically, each of the foregoing references dis-closes preparative techniques that require extreme conditions 26 or relatively sophisticated or complicated handling; and, 27 each of the techniques often fail to yield suitable products.
28 For example, insertion of lithium in the metal dichalcogen-29 ides by the foregoing techniques typically results in less than 0~7 moles of lithium being inserted in the metal dichal-31 cogenide Often multiphase products result which include un-32 wanted molecules, such as ammonia or nitrogenous contaminants, - 2 _ ~
104~3'7 1 being inserted within the planes of the transition metal 2 chalcogenide.
3According to the present invention there is pro-4 vided a method of lithiating metal chalcogenides under con-trolled conditions. In its simplest sense, the method of 6 the instant invention compr~ses adding a specific lithium 7 compound to a transition metal chalcogenide. The specific 8 lithium compound i8 selected from the group con isting of 9LiRl, LiC(Rl)3, LiN(Rl)2~ L~BH(Rl)3, LiRl-R2 and LiALH4-R2 lo wherein Rl is a hydrocarbon radical havlng from l to 8 11 carbon atoms and R2 is a chelating polyam~ne~ Typical hy-12 drocarbon radicals lnclude vinyl, butyl, phenyl, methyl and 13 ethyl radicalsO Preferred chelating polyamine~ include tetramethylethylene diamine and pentamethyldiethylene tri-amine. The metal chalcogenide to which the reactive lith-16 ium compound is added has the general formula MZy wherein Z
17 is an element selected from the group consisting of sulfur, 18 selenium and tellurium; y i8 a number between l.0 and 4O0 19 and M is an element selected from the group consisting of Group IVB elements, Group VB elements, molybdenum, tungsten, 21 technetium, pLatinum, rhenium, germanium, tin and lead but 22 not vanadium when Z is sulfur and y is 2. Preferably, M
23 in the formula MZy is titanlum or tantalum (e~pecially ti-24 tanium); Z is preferably sulfur or selenium (especially pre-ferred is sulfur), and3 y preferably has a numerical value 26between abo~t 1.60 and about 2.02, especlally 2Ø
27In another aspect of the present invention, there 28 is provided novel lithium intercalated metal chalcogenides 29 having the general formula LixMZy wherein Z is sulfur and selenium; M i~ an element selected from Group VB elements, 31 hafnium and zirconium but not vanadium when Z is sulfur; y 32is a numerical value between 1.67 and 2.02 and x is a numer-104~Z3'7 l ical value between 0.8 and 1.2 and preferably 009 to l~lo 2 In yet another aspect of the present invention 3 there is prov~ded a nitrogen-free lithium titanium sulfide 4 of the formula LiXTiSy where x is a numerical value from 0.8 to 1.2; and preferably 0.9 to 1.1 and y is a numerical 6 value from 1~67 to 2.02.
7 In the practice of the present inventlon metal 8 chalcogenide~ are lithiated under controlled conditions by 9 adding a specific lithium compound to a met~l chalcogenide The lithium compound employed i8 selec~ed from the group 11 consisting of LiRl, LiC(Rl)3, LiN~R1~2, LiRloR2 and l2 LiALH4-R2 wherein Rl is a hydrocarbon radical having from 3 1 to 8 carbon atoms and R2 is a chelating polyamine~ Typi-14 cal hydrocarbon radicals include vinyl, butyl,phenyl, methyl, ethyl and the like. Typical chelating polyamines include l6 tetramethylethylene di~mine, pentamethyldiethylene triamine 17 and hexamethyltriethylene tetramine. In the preferred em-18 bodiment of the present invention3 the lithium compound is 19 n-butyl lithium.
The foregoing l~thium compounds are prepared by 21 wel~knor~n techniques which form no part of the present in-22 vention. Indeed, the preferred lithium compound, as well 23 as others, is a commercially available compound.
24 In general, the lithium compound is dissolved in an aprotic solvent or diluent such as hexane, heptane, ben-26 zene, toluene or tetrahydrofuran. Then, the solution of the -27 lithium compound is added to the metal chalcogenide, at a 28 temperature in the range of from about -100S. to 100C., 29 and preferably at ambient tempera~ures~ The mixture is al-lowed to stand (stirring is optional) for a time sufficient 31 for lithiation of the metal chalcogenide to occur. Generally, 32 such reaction time i8 between a half day to 30 days or more.
-104~Z37 1 While stirring tends to speed the lithiation of the metal 2 chalcogenide, stirring also tends to promote the formation 3 of powdered productsO Thus, if the crystal size of metal 4 chalcogenide is to be substantially maintained stirring the mixture i8 not preferred~
6 As will be appreciated the specific lithium com-7 pounds are generally air or moisture sensitive and conse~
8 quently the lithium compound and the metal chalcogenide are 9 handled in inert gas atmo~pheres, such as nitrogen, helium o or argon.
1 Although a stoichiometric amount of the lithium 12 compound and metal chalcogenide can be used, it is preferred in the practice of the pre~ent invention to use an excess of the specific lithium compound~ For example~ it is particu-larly preferred to use a 50% mole excei~ of the lithium 16 compound.
17 The reaction can be followed by assaying a ~uper-8 natant liquid for basic lithium or in the case of when n 19 butyl lithium is employed as the lithium compound, the ex-tent of reaction also can be followed by monitor~ng the re-21 action mixture for the formation of octane, a coproduct.
22 Generally, the reaction i8 carried out at atmos-23 pheric pressure, although pressures up to 5 atmospheres or 24 more may be employed.
As indic~ted previously, the metal chalcogenide 26 employed in the pre~ent invention ha~ the general formula 27 MZy wherein M is an element selected from the group consist-28 ing of Group IYB elements, Group VB elements, molybdenum, 29 tungsten, technetium, platinum, rhenium, germanium, tin and lead, Z i~ a chalcogen, i.e. Z is an element selected from 31 the group consisting of sulfur, selenium and tellurium; and 32 y has a numerical value between l.0 and about 4.0; provided, ~ 5 -lO~t~Z37 1 however, that when M i8 vanadium and y is 2, Z is selenium 2 and tellurium onlyO
3 The term "Group" refers to the particular Group 4 of the Pericdic Table of the Elements of the type set forth
5 on the inside cover of The Merck Index (7th ed,)0
6 The foregoing metal chAlcogenide~ are readily pre-
7 pared by well known techniques such as heating the elements
8 at elevated temperatures in the requisite ratio~ or by meta-
9 thetical reaction~ of the metal halides with hydrogen sulfide 0 and the like. Many of these metal chalcogenides are commer-11 cially available al80.
12 The lithium intercalated metal chalcogenides of ~-13 the present invention may be utilized as cathode active ma-14 terials in batteries.
15 EXAMPLE 1 - Reaction of the Metal Chalco~enide with n-butyl . .
l6 Lithium 7 In the followi~g example n-butyl lithium was em-8 ployed as the reactive lithium compound for lithiating the 19 metal chalcogenide~ The n~butyl lithium employed was a com- -mercially available material of approximately 106 molar in 21 normal hexane, In most ln~tances this-commerc~ally avail-22 able n-butyl lithium was diluted further with hexane to 23 provide a ~olution approximately 0.1 molar.
24 Prior to use, the precise concentration of n-butyl lithium starting reagent was determined by withdrawing an 26 aliquot in a dry box, allowing the solvent to evaporate in 27 a hood and quenching the remaining white material with ethan-28 ol and then water, A few drops of phenolphthalein indicator 29 solution were added to the hydrolysate and the resultant solution was back titrated by first adding excess .LN HCl 31 and then neutralizing with standard base~
32 To a known am3unt of the transition metal chalco-. - .
,: . . .: .
- . :. - .
104~;~37 1 genide was added .5 molar excess of the hexane solution of 2 n-butyl lithium. The material wa~ kept for a period of be-3 tween three days and three weeks under ambient condition~ in 4 a dry box. The reaction mixture wa~ then filtered and a S solid material washed once with normal hexane that had been 6 distilled from P205. The collected filtrate waæ assayed 7 and the amount of lithium that reac,ed with the metal chal-8 cogenide W~8 inferret by loss of active ba~e. The inferred 9 lithium content was also checked by chemical analysi~ of 1~ representative ~ample~ of lithiated product~; and these 11 chemical analysis compared favorably with inferred results.
l2 For example, TiS2 and TaS2 were lithiated in the manner set 13 forth above and it was found that sub~t nt~ally one moie of 14 lithium reacted with one mole of metal chalcogenide based on unreacted n-butyl lithium. Direct chemical analysis was l6 as follows: LiTiS2 Calc. Li:5.88%, found: 5.79, 5.98, 5.8770;
17 LiTaS2 Calc. Li:2.78%, found 2.75, 2~62%.
18 The results of the foregoing experiments are given 19 below in Tabl~ I.
TABLE I
21 Met~l Chalco~enide Product 22 TaS2 Lio~g4Tas2 23 TiS2 Lil,03Tis2 24 Til.lS2 Lio,88Til.lS2 Til.l6S2 Lio 68Tilol6S2 26 ZrS2 LiloOZrS2 27 HfS2 Lil.lHfS2 28 NbS2 Lioo8NbS2 29 MoS2 Lil 06MS2 WS2 LiO.26WS2 31 TiSe2 Lio~g7~ise2 32 ZrSe2 Lil,l2Zrse2 ' 104~237 2 Metal Chalcogenide Pr~uce 3 VSe2 Lil OVSe2 ~ -4 NbSe2 LilooNbse2 HfSe2 Lio 97HfSe2 6 TaSe2 Lioo88T~se2 7 TiTe2 Lioo8TiTe2 8 HfTe2 Lioo54HfTe2 9 VTe2 Lilo 71VTe2 MoTe2 Lio 36MoTe2 WSe2 Lil 5WSe 1~ MoSe2 Lioo 5Mo~e2 13 ReSe2 Lilol6Rese2 14 PtSe2 Lil 48Pt~e2 V5S8 LiO,34V5S8 16 TiS3 L~3,oTiS3 ~-17 Z~S3 Li4,sZrs3 8 ZrSe3 Li4 7~rS~3 19 HfS3 Li2.5HfS3 HfSe3 Li2OgHfSe8 21 NbS3 Li2o22NbS3 22 NbSe3 Li3,16NbSe3 23 Bi2Te3 Lilo26Bi2Te3 24 vs4 Li2VS4 GaS Lio 2GaS
26 * only 1 mole equivalent of n-butyl lithium added 27 A~ will be appreciated from an examination of the 28 foregoing table,--the method of the present invention gives :
.
29 lithiated metal chalcogenides of unusually high lithium con-tent. Indeed x-r8y diffraction powder patterns verify that 31 the novel compositions of the formula ~iXMZy where Z is ~ul-32 fur and selenium; M is an element selected from~Group VB
- 8 - :
104~;~37 1 elements titanium, zirconium, hafnium but not vanadium when 2 Z is sulfur, x is from 008 to lo 2 and y is a value from 1.67 3 to 2.02; are intercalated species; i.e. the x~ray data show~
4 the presence of intercalated phases.
6 This example demon~rates the use of other lithium 7 compounds in the formation of intercalated lith~um chalco-8 genides.
9 The procedure used followed substantially that of Example 1. The test conditions and results are summarized 11 in Table II.
l2 BLE II
13 Lithium Compound Solvent Product 14 LiN(CH3)2 Ben~ene LiXTiS2 LiBH~C2Hs)3 THF LixTaS2 16 Li n-butyl-TMEDA Hexane LixTaS~
17 LiALH4-PMDT Benzene LixTaS2 18 Li C6H5 Benzene L ~TaS2 19 Li C2H3(Vinyl~ THF L~xTaS2 Li CsHs(cyclopentadienyl) THF LixTaS2 21 LiC(C6HS)3 Hexane L ~TaS2 22 PMDT = pentamethyldiethylene triamine 23 TMEDA ~ tetramethylethylene diamine 24 The value of x in the foregoing products ranged from Ool to 1Ø Intercalation of the chalcogenide was also 26 verified by x~ray powder diffraction patterns~
28 This example demonstrates a very significant fea-29 ture of the present invention by comparing lithium inter-calated titanium disulfide prepared by a prior art process 31 utilizing a solution of lithium metal in liquid ammonia and 32 utilizing n-butyl lithium as disclosed herein~
; g _
12 The lithium intercalated metal chalcogenides of ~-13 the present invention may be utilized as cathode active ma-14 terials in batteries.
15 EXAMPLE 1 - Reaction of the Metal Chalco~enide with n-butyl . .
l6 Lithium 7 In the followi~g example n-butyl lithium was em-8 ployed as the reactive lithium compound for lithiating the 19 metal chalcogenide~ The n~butyl lithium employed was a com- -mercially available material of approximately 106 molar in 21 normal hexane, In most ln~tances this-commerc~ally avail-22 able n-butyl lithium was diluted further with hexane to 23 provide a ~olution approximately 0.1 molar.
24 Prior to use, the precise concentration of n-butyl lithium starting reagent was determined by withdrawing an 26 aliquot in a dry box, allowing the solvent to evaporate in 27 a hood and quenching the remaining white material with ethan-28 ol and then water, A few drops of phenolphthalein indicator 29 solution were added to the hydrolysate and the resultant solution was back titrated by first adding excess .LN HCl 31 and then neutralizing with standard base~
32 To a known am3unt of the transition metal chalco-. - .
,: . . .: .
- . :. - .
104~;~37 1 genide was added .5 molar excess of the hexane solution of 2 n-butyl lithium. The material wa~ kept for a period of be-3 tween three days and three weeks under ambient condition~ in 4 a dry box. The reaction mixture wa~ then filtered and a S solid material washed once with normal hexane that had been 6 distilled from P205. The collected filtrate waæ assayed 7 and the amount of lithium that reac,ed with the metal chal-8 cogenide W~8 inferret by loss of active ba~e. The inferred 9 lithium content was also checked by chemical analysi~ of 1~ representative ~ample~ of lithiated product~; and these 11 chemical analysis compared favorably with inferred results.
l2 For example, TiS2 and TaS2 were lithiated in the manner set 13 forth above and it was found that sub~t nt~ally one moie of 14 lithium reacted with one mole of metal chalcogenide based on unreacted n-butyl lithium. Direct chemical analysis was l6 as follows: LiTiS2 Calc. Li:5.88%, found: 5.79, 5.98, 5.8770;
17 LiTaS2 Calc. Li:2.78%, found 2.75, 2~62%.
18 The results of the foregoing experiments are given 19 below in Tabl~ I.
TABLE I
21 Met~l Chalco~enide Product 22 TaS2 Lio~g4Tas2 23 TiS2 Lil,03Tis2 24 Til.lS2 Lio,88Til.lS2 Til.l6S2 Lio 68Tilol6S2 26 ZrS2 LiloOZrS2 27 HfS2 Lil.lHfS2 28 NbS2 Lioo8NbS2 29 MoS2 Lil 06MS2 WS2 LiO.26WS2 31 TiSe2 Lio~g7~ise2 32 ZrSe2 Lil,l2Zrse2 ' 104~237 2 Metal Chalcogenide Pr~uce 3 VSe2 Lil OVSe2 ~ -4 NbSe2 LilooNbse2 HfSe2 Lio 97HfSe2 6 TaSe2 Lioo88T~se2 7 TiTe2 Lioo8TiTe2 8 HfTe2 Lioo54HfTe2 9 VTe2 Lilo 71VTe2 MoTe2 Lio 36MoTe2 WSe2 Lil 5WSe 1~ MoSe2 Lioo 5Mo~e2 13 ReSe2 Lilol6Rese2 14 PtSe2 Lil 48Pt~e2 V5S8 LiO,34V5S8 16 TiS3 L~3,oTiS3 ~-17 Z~S3 Li4,sZrs3 8 ZrSe3 Li4 7~rS~3 19 HfS3 Li2.5HfS3 HfSe3 Li2OgHfSe8 21 NbS3 Li2o22NbS3 22 NbSe3 Li3,16NbSe3 23 Bi2Te3 Lilo26Bi2Te3 24 vs4 Li2VS4 GaS Lio 2GaS
26 * only 1 mole equivalent of n-butyl lithium added 27 A~ will be appreciated from an examination of the 28 foregoing table,--the method of the present invention gives :
.
29 lithiated metal chalcogenides of unusually high lithium con-tent. Indeed x-r8y diffraction powder patterns verify that 31 the novel compositions of the formula ~iXMZy where Z is ~ul-32 fur and selenium; M is an element selected from~Group VB
- 8 - :
104~;~37 1 elements titanium, zirconium, hafnium but not vanadium when 2 Z is sulfur, x is from 008 to lo 2 and y is a value from 1.67 3 to 2.02; are intercalated species; i.e. the x~ray data show~
4 the presence of intercalated phases.
6 This example demon~rates the use of other lithium 7 compounds in the formation of intercalated lith~um chalco-8 genides.
9 The procedure used followed substantially that of Example 1. The test conditions and results are summarized 11 in Table II.
l2 BLE II
13 Lithium Compound Solvent Product 14 LiN(CH3)2 Ben~ene LiXTiS2 LiBH~C2Hs)3 THF LixTaS2 16 Li n-butyl-TMEDA Hexane LixTaS~
17 LiALH4-PMDT Benzene LixTaS2 18 Li C6H5 Benzene L ~TaS2 19 Li C2H3(Vinyl~ THF L~xTaS2 Li CsHs(cyclopentadienyl) THF LixTaS2 21 LiC(C6HS)3 Hexane L ~TaS2 22 PMDT = pentamethyldiethylene triamine 23 TMEDA ~ tetramethylethylene diamine 24 The value of x in the foregoing products ranged from Ool to 1Ø Intercalation of the chalcogenide was also 26 verified by x~ray powder diffraction patterns~
28 This example demonstrates a very significant fea-29 ture of the present invention by comparing lithium inter-calated titanium disulfide prepared by a prior art process 31 utilizing a solution of lithium metal in liquid ammonia and 32 utilizing n-butyl lithium as disclosed herein~
; g _
10~j237 1 The LiTiS2 prepared via n~butyl lithium followed 2 the procedure of Example 1. The LiTiS2 prepared in liquid 3 ammonia was made as followso 4 A glass pressure tube fitted with a valve was loaded with 2.000 g (0.01786 moles) TiS2 and 0~125 g 6 (0.01786 moles~ Li cut into 1/4 inch piece~0 Then 10 ml 7 of freshly distilled a D nia (from sodium~ was condensed 8 into the tube and the valve closed. The tube was allowed 9 to warm to ambient temperature (about 22G.)~ After 2 hours the ammonia was allowed to evaporate, The remaining
11 ~olid was heated to about 250Co in a vacuum of le~s than about 10 2 torr. for a period of about 0~5 hrO Chemical l3 analysis of the product i~ given in Table III belowO
15Element L Found% Calculated for LiTiS2 l6 Ti 39.75 40.33 l8 Li 5.55 5.88 21 As can be seen the LiTiS2 material prepared in 22 liquid ammonia contained more than 3.5% by weight of nitro-23 gen-hydrogen contaminant despite the attempts to completely 24 remove the nitrogen~hydrogen contaminant. The presence of protons is also confirmed by nuclear magnetic resonance 26 analysis. Indeed, using tran~lent solid~state nmr tech-27 nique~, the lithium spin lattice relaxation times were meas-28 ured and the self-diffusion coefficient of the lithium was 29 deternined for the sample of LiTiS2 prepared with n butyl lithium in accordance with this invention and for the 31 LiTiS2 sample prepared in liquid a D nia as described above.
32 The self-diffusion coefficient for the nbutyl lithium pro-~04~Z37 1 duct Wa8 equal to 10~9cm2/sec. wherea~ for the liquid ammon-2 ia product it was less than 2 x 10~1cm2/sec. This data 3 shows that the lithium in the LiTiS2 product of the present 4 invention is diffusing at least five times faster than the lithium in the amminated productO
6 Additionally, the nitrogen-hydrogen contaminant, 7 mentioned above 9 adversely ~ffects the crystallinity of 8 lithium intercalated metal chalcogenide~ This is shown 9 very dramatically in the ~ide by side comparison o the attached electron microphotographs having a magnification 11 factor of 3000, of samples of lithium intercalated TiS2 l2 according to this invention and the prior artO m e mAterial l3 prepared according to this invention i~ free of nitrogen-14 hydrogen contaminants and is highly crystalline, whereas the material prepared by the prior art technique is not l6 truly LiTiS2 but i8 an aminated species of LiTiS2 that is extremely exfoliatedO
18 EXAMPLE _ l9 This example illustrates the utility of the inter-calated chalcogenides of the present invention.
21 Lithium titanium sulfide, Lil oTiS2 was prepared 22 by adding 0.51 grams of titanium disulfide powder to 4 ml 23 of 106 molar solution of n-butyl lithium in normsl hexane 24 and allowing the mixture to stand for several days in a nitrogen atmosphere. About 15 milligrams of the LilooTiS2 26 prepared is pressed onto a copper plate of 005 inches in 27 dlameter~ This plate was covered with a piece of filter 28 paper as a separator and mounted ln a "teflon" holderO A
29 few milliliters of saturated solution of lithium hexafluoro- :
phosphate in propylene carbonate were poured into the holder 3l followed by a lithium strip anode of dimensions 0.4 x 2.0 x 32 0.5 cm~ A copper plunger wa8 then screwed down tight into 104~Z37 1 the "teflo~" holder. The cell electric contacts were made 2 through the copper plate and plunger.
3 The initial open circuit voltage of this cell was 4 1.87 V. An attempt to further discharge the cell at a con~
~tant current of 0.2 ma. caused a rapid fall in the cell 6 voltage, indicating tha~ the sy~tem was es~entially fully 7 discharged. Recharging at 113 maO was accomplished at ap~
8 plied voltages in the range of 2.4 to 3.1 Yolt~O
15Element L Found% Calculated for LiTiS2 l6 Ti 39.75 40.33 l8 Li 5.55 5.88 21 As can be seen the LiTiS2 material prepared in 22 liquid ammonia contained more than 3.5% by weight of nitro-23 gen-hydrogen contaminant despite the attempts to completely 24 remove the nitrogen~hydrogen contaminant. The presence of protons is also confirmed by nuclear magnetic resonance 26 analysis. Indeed, using tran~lent solid~state nmr tech-27 nique~, the lithium spin lattice relaxation times were meas-28 ured and the self-diffusion coefficient of the lithium was 29 deternined for the sample of LiTiS2 prepared with n butyl lithium in accordance with this invention and for the 31 LiTiS2 sample prepared in liquid a D nia as described above.
32 The self-diffusion coefficient for the nbutyl lithium pro-~04~Z37 1 duct Wa8 equal to 10~9cm2/sec. wherea~ for the liquid ammon-2 ia product it was less than 2 x 10~1cm2/sec. This data 3 shows that the lithium in the LiTiS2 product of the present 4 invention is diffusing at least five times faster than the lithium in the amminated productO
6 Additionally, the nitrogen-hydrogen contaminant, 7 mentioned above 9 adversely ~ffects the crystallinity of 8 lithium intercalated metal chalcogenide~ This is shown 9 very dramatically in the ~ide by side comparison o the attached electron microphotographs having a magnification 11 factor of 3000, of samples of lithium intercalated TiS2 l2 according to this invention and the prior artO m e mAterial l3 prepared according to this invention i~ free of nitrogen-14 hydrogen contaminants and is highly crystalline, whereas the material prepared by the prior art technique is not l6 truly LiTiS2 but i8 an aminated species of LiTiS2 that is extremely exfoliatedO
18 EXAMPLE _ l9 This example illustrates the utility of the inter-calated chalcogenides of the present invention.
21 Lithium titanium sulfide, Lil oTiS2 was prepared 22 by adding 0.51 grams of titanium disulfide powder to 4 ml 23 of 106 molar solution of n-butyl lithium in normsl hexane 24 and allowing the mixture to stand for several days in a nitrogen atmosphere. About 15 milligrams of the LilooTiS2 26 prepared is pressed onto a copper plate of 005 inches in 27 dlameter~ This plate was covered with a piece of filter 28 paper as a separator and mounted ln a "teflon" holderO A
29 few milliliters of saturated solution of lithium hexafluoro- :
phosphate in propylene carbonate were poured into the holder 3l followed by a lithium strip anode of dimensions 0.4 x 2.0 x 32 0.5 cm~ A copper plunger wa8 then screwed down tight into 104~Z37 1 the "teflo~" holder. The cell electric contacts were made 2 through the copper plate and plunger.
3 The initial open circuit voltage of this cell was 4 1.87 V. An attempt to further discharge the cell at a con~
~tant current of 0.2 ma. caused a rapid fall in the cell 6 voltage, indicating tha~ the sy~tem was es~entially fully 7 discharged. Recharging at 113 maO was accomplished at ap~
8 plied voltages in the range of 2.4 to 3.1 Yolt~O
12 ~
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of lithiating metal chalcogenides of the formula MZy wherein:
M is an element selected from Group IVB, Group VB
elements of the Periodic Table of the Elements, molybdenum, tungsten, technetium, platinum, rhenium, germanium, tin and lead;
y is a numerical value between about 1.0 and about 4.0; and Z is an element selected from the group consisting of sulfur, selenium and tellurium, provided that when M is vanadium and y is 2, Z is selected from selenium and tellur-ium only; comprising adding at least a stoichiometric amount of a lithium compound to said metal chalcogenide, said lithium compound being selected from the group consisting of LiR1, LiC(R1)3, LiN(R1)2, LiBH(R1)3, LiR1.R3 and LiAlH4.R2 wherein:
R1 is a hydrocarbon radical having 1 to 8 carbon atoms and R2 is a chelating polyamine.
M is an element selected from Group IVB, Group VB
elements of the Periodic Table of the Elements, molybdenum, tungsten, technetium, platinum, rhenium, germanium, tin and lead;
y is a numerical value between about 1.0 and about 4.0; and Z is an element selected from the group consisting of sulfur, selenium and tellurium, provided that when M is vanadium and y is 2, Z is selected from selenium and tellur-ium only; comprising adding at least a stoichiometric amount of a lithium compound to said metal chalcogenide, said lithium compound being selected from the group consisting of LiR1, LiC(R1)3, LiN(R1)2, LiBH(R1)3, LiR1.R3 and LiAlH4.R2 wherein:
R1 is a hydrocarbon radical having 1 to 8 carbon atoms and R2 is a chelating polyamine.
2. The method of claim 1 wherein said lithium com-pound is added to said metal chalcogenide at a temperature ranging from about -100°C. to about 100°C.
3. The method of claim 1 wherein said lithium compound is n-butyl lithium.
4. The method of claim 1 wherein M is selected from Ti and Ta; Z is selected from S and Se; and y is be-tween about 1.67 and about 2.02.
5. The method of claim 1 wherein said chelating polyamine is selected from tetramethylethylene-diamine and pentamethyldiethylene triamine.
6. A lithium intercalated metal chalcogenide having the formula LixMZy wherein:
M is selected from Group VB elements, Ti, Hf and Zr;
Z is selected from S and Se, provided that when M is vanadium Z is Se;
y is between 1.67 and 2.02; and x is between 0.8 and 1.2.
M is selected from Group VB elements, Ti, Hf and Zr;
Z is selected from S and Se, provided that when M is vanadium Z is Se;
y is between 1.67 and 2.02; and x is between 0.8 and 1.2.
7. The lithium intercalated metal chalcogenide of claim 6 wherein x is between 0.9 and 1.1.
8. The lithium intercalated metal chalcogenide of claim 6 wherein M is Ti, Z is S and said chalcogenide is free of nitrogen contaminants.
9. The lithium intercalated metal chalcogenide of claim 6 wherein M is Ta and Z is S.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48786074A | 1974-07-12 | 1974-07-12 | |
| US05/510,383 US3933688A (en) | 1974-07-12 | 1974-09-30 | Method for lithiating metal chalcogenides and intercalated products thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1046237A true CA1046237A (en) | 1979-01-16 |
Family
ID=27049149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA226,256A Expired CA1046237A (en) | 1974-07-12 | 1975-05-05 | Method for lithiating metal chalcogenides and intercalated products thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3933688A (en) |
| JP (1) | JPS5948762B2 (en) |
| CA (1) | CA1046237A (en) |
| DE (1) | DE2530068C2 (en) |
| FR (1) | FR2277898A1 (en) |
| GB (1) | GB1499523A (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094893A (en) * | 1976-11-24 | 1978-06-13 | Exxon Research & Engineering Co. | Isonitrile intercalation complexes |
| US4203861A (en) * | 1977-12-01 | 1980-05-20 | Laporte Industries Limited | Inorganic compounds |
| US4132620A (en) * | 1978-02-02 | 1979-01-02 | Diamond Shamrock Technologies S.A. | Electrocatalytic electrodes |
| US4166160A (en) * | 1978-03-06 | 1979-08-28 | Exxon Research & Engineering Co. | Cells having cathodes derived from ammonium-molybdenum-chalcogen compounds |
| NL187943C (en) * | 1978-08-21 | 1992-02-17 | Moli Energy Ltd | METHOD FOR CONDITIONING A SECONDARY ELEMENT INCLUDING A LITHIUM ANODE, A NON-AQUEOUS ELECTROLYTE AND A METAL CHALCOGENIDE CATHODE |
| FR2465326A1 (en) | 1979-09-11 | 1981-03-20 | Comp Generale Electricite | NON-AQUEOUS ELECTROLYTE ELECTROCHEMICAL GENERATOR |
| FR2465327A1 (en) * | 1979-09-11 | 1981-03-20 | Comp Generale Electricite | NON-AQUEOUS ELECTROLYTE ELECTROCHEMICAL GENERATOR |
| US4414142A (en) * | 1980-04-18 | 1983-11-08 | Vogel F Lincoln | Organic matrix composites reinforced with intercalated graphite |
| US4376709A (en) * | 1980-11-10 | 1983-03-15 | Exxon Research And Engineering Co. | Intercalated layered mixed oxides |
| JPS5950011A (en) * | 1982-09-10 | 1984-03-22 | Central Glass Co Ltd | Three-component interlaminar graphite compound consisting of graphite, alkali metallic fluoride and fluorine, its manufacture, and electrically conductive material made of it |
| JPS5990363A (en) * | 1982-11-15 | 1984-05-24 | Matsushita Electric Ind Co Ltd | Solid secondary battery |
| US4481267A (en) * | 1983-04-01 | 1984-11-06 | Duracell Inc. | Insoluble heavy metal polysulfide cathodes |
| US4853359A (en) * | 1986-04-23 | 1989-08-01 | Simon Fraser University | Novel transition metal dichalcogenide catalysts |
| US5351164A (en) * | 1991-10-29 | 1994-09-27 | T.N. Frantsevich Institute For Problems In Materials Science | Electrolytic double layer capacitor |
| IL103580A0 (en) * | 1991-10-29 | 1993-03-15 | Ivan D Kozmik | Energy storage device |
| US5298349A (en) * | 1992-03-02 | 1994-03-29 | Wilson Greatbatch, Ltd. | Method of pretreating a cathode for attaining a stable voltage upon cell assembly |
| US5567401A (en) * | 1995-03-14 | 1996-10-22 | Doddapaneni; Narayan | Method of producing stable metal oxides and chalcogenides and power source |
| US7060650B2 (en) * | 2002-02-04 | 2006-06-13 | Rendina David D | Hydrogenation catalysts and methods |
| US8110522B2 (en) * | 2008-09-25 | 2012-02-07 | Range Fuels, Inc. | Methods for promoting syngas-to-alcohol catalysts |
| US9409792B2 (en) | 2014-10-29 | 2016-08-09 | Toyota Motor Engineering & Manufacturing North America, Inc. | Solventhermal synthesis of nanosized two dimensional materials |
| CN113896227A (en) * | 2021-10-27 | 2022-01-07 | 苏州大学 | Two-dimensional chalcogenide compound and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3791867A (en) * | 1972-07-24 | 1974-02-12 | Bell Telephone Labor Inc | Rechargable nonaqueous battery |
-
1974
- 1974-09-30 US US05/510,383 patent/US3933688A/en not_active Expired - Lifetime
-
1975
- 1975-05-05 CA CA226,256A patent/CA1046237A/en not_active Expired
- 1975-05-09 GB GB19649/75A patent/GB1499523A/en not_active Expired
- 1975-06-11 JP JP50069777A patent/JPS5948762B2/en not_active Expired
- 1975-07-05 DE DE2530068A patent/DE2530068C2/en not_active Expired
- 1975-07-09 FR FR7521579A patent/FR2277898A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5948762B2 (en) | 1984-11-28 |
| DE2530068C2 (en) | 1983-12-22 |
| DE2530068A1 (en) | 1976-01-29 |
| US3933688A (en) | 1976-01-20 |
| JPS519096A (en) | 1976-01-24 |
| FR2277898A1 (en) | 1976-02-06 |
| FR2277898B1 (en) | 1980-07-04 |
| GB1499523A (en) | 1978-02-01 |
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