CN1074249A - The layered crystal material of energy load a large amount object - Google Patents
The layered crystal material of energy load a large amount object Download PDFInfo
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- CN1074249A CN1074249A CN92113391A CN92113391A CN1074249A CN 1074249 A CN1074249 A CN 1074249A CN 92113391 A CN92113391 A CN 92113391A CN 92113391 A CN92113391 A CN 92113391A CN 1074249 A CN1074249 A CN 1074249A
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- bismuth
- chalkogenide
- folder
- lithium
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- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000013078 crystal Substances 0.000 title claims description 44
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- 230000007547 defect Effects 0.000 claims abstract description 22
- 239000002178 crystalline material Substances 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 9
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 53
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 43
- 239000003708 ampul Substances 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 238000005476 soldering Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims 5
- 239000005864 Sulphur Substances 0.000 claims 1
- 230000003064 anti-oxidating effect Effects 0.000 claims 1
- -1 bismuth chalcogenide Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims 1
- RBWFXUOHBJGAMO-UHFFFAOYSA-N sulfanylidenebismuth Chemical compound [Bi]=S RBWFXUOHBJGAMO-UHFFFAOYSA-N 0.000 claims 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229910052798 chalcogen Inorganic materials 0.000 description 4
- 150000001787 chalcogens Chemical class 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004857 zone melting Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- OMEPJWROJCQMMU-UHFFFAOYSA-N selanylidenebismuth;selenium Chemical compound [Se].[Bi]=[Se].[Bi]=[Se] OMEPJWROJCQMMU-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention provides a kind of crystalline material and manufacture method thereof, this material can a large amount of load mol ratios greater than 3 object, and show that Gibbs free energy function and object concentration have nothing to do.This crystalline material belongs to Me
yCh
xClass, wherein Me is selected from Bi and Sb, and Ch is selected from Te, Se and S, Y is 1 or 2, and Z is in 1 to 3 scope, so the defect concentration of this material is low as to be enough to allow in the Fan Dewaersi groove, every mole of described material is layer folder 3 mole of lithium at least, and there is no obvious lattice distortion.The present invention can provide the layer folder material of a kind of object load up to 10 moles/mole main bodys.
Description
The application is the part continuation application of No. 07/784,525, the U. S. application submitted on October 29th, 1991.
The present invention relates to the height zero defect monocrystal material of ergosphere folder a large amount object thing, and relate to the manufacture method of this material.The present invention and then relate to height and be mingled with the stratiform crystalline material.
Layered crystal material (main body) can hold exotic (object) in the interlayer groove, thus form layers folder material.The compound that the interlayer embedding is assorted, for example the chalkogenide of graphite and transition metal has thoroughly been studied recent two decades, and is applied in a lot of fields, comprising battery, photocell, superconduction and hydrogen storage.
The main body that the application considered has the anisotropy layered structure that separates with the Fan Dewaersi groove, can hold small object particle such as lithium or hydrogen in this groove.Because the faint property of Vander Waals attraction, Fan Dewaersi space (groove) is easy to admit external object thing, no matter is electroneutral or charged object thing.Object thing filling groove is until the more position of unable acquisition.The object thing amount that occupies the Fan Dewaersi position is the object weight bearing power." load " or " weight bearing power " is defined herein as the object thing mole number of every mole of material of main part; Object " thing " is defined as the ion of element or charge atom not.People generally acknowledge, for many application, improve the weight bearing power that object enters stratified material, then can significantly improve the performance of device.
The distortion of layered crystal material often is used to increase groove width, thereby increases the object load.US4,288,508 have reported a kind of active material of cathode of battery, and the chemical formula of its preferred thing is Li
zNa
yTiS
2, wherein the scope of Y is 0.15-0.20, Z can be up to 3.25.Yet in these materials, increasing load is to pry open the Fan Dewaersi groove with bigger sodium atom to realize.This has just caused TiS
2The remarkable distortion of lattice.
US4,309,491 have reported a kind of sosoloid that contains the chalcogenide bismuth as active material of cathode.It is said that object load process need is up to 6 Faraday's electronics in the chalkogenide of bismuth, so can set, layer has pressed from both sides 6 moles of objects.But it is said that also sparking voltage has very big dependency to object concentration.In addition, do not show that the bismuth chalkogenide that makes is the height trouble-free state with controlled lattice parameter.
Therefore, the objective of the invention is, a kind of ergosphere of confession presss from both sides high especially object thing load, wherein gibbs free energy changeization (△ G) is pressed from both sides the irrelevant monocrystal material of substrate concentration with layer basically.Under these conditions, depend on the character of △ G, for example the operating potential of electrochemical cell remains unchanged.
Another object of the present invention is that a kind of crystalline material with height layer folder of controlled lattice parameter is provided.
A further object of the invention is, provides a kind of preparation to have controlled lattice parameter that can height load object, the method for height zero defect monocrystal material.
The present invention has overcome the limitation of prior art by a kind of height clear-stuff with controlled patterned features is provided.When this material is used for battery and so on device, can obtain surpassing the excellent properties of existing device.
One aspect of the present invention provides a kind of lamellar single crystal material, and its defect concentration is low as to be enough to the every mole of possible layer folder of material at least 3 mole of lithium in the Fan Dewaersi groove, and lattice is obviously distorted.Another feature of this material is that its gibbs free energy changeization is basic and lithium layer folder concentration is irrelevant.
Another face of the present invention, it is Me that a kind of chemical formula is provided
yCh
zMonocrystal material, Me is selected from Bi and Sb in the formula, Ch is selected from Te, Se and S, Y is 1 or 2, Z is 1,2 or 3.The defect concentration of this material low be enough to might be in the Fan Dewaersi groove layer folder 3 mole of lithium at least, and lattice is obviously distorted.Another feature of this material is that △ G is basic and lithium layer folder concentration is irrelevant.About layer folder compound with use the further details of the device of these compounds, submit and support application for referencial use in the lump at same date mutually with the application's (" layered crystal material of energy load a large amount object ") below being set forth in: " energy storage device ", " double-layer electrolytic capacitor " and " electric capacity electrothermal device " at this.
In each preferred embodiment, this material tool hexagonal lattice structure, defect concentration is lower than 10
12/ cm
3, and the direction of interior impurity defect distribution gradient of Fan Dewaersi groove and lithium layer folder is inversely proportional to.Being characterised in that in addition of this monocrystal material, the cohesion of lithium occur in weight bearing power and are roughly under 3 the situation.Cohesion is to become semi liquid state by lattice gas.Crystalline network can be rhombohedron or hexahedron structure.This monocrystal material is single crystal preferably.In each preferred embodiment, through careful CONTROL PROCESS defect concentration is reduced to minimum degree, make crystal lattices complete.In other preferred embodiments, monocrystal material is used for battery, electrical condenser or thermoelectric element; Certainly, but monocrystal material also grinding powder be used for some device.
Another aspect of the present invention, the method for preparing high purity bismuth chalkogenide comprises the following steps: to load the sulfur family element and the bismuth of stoichiometric quantity in ampoule; Be filled with the atmosphere of selecting to prevent oxidation in the ampoule, soldering and sealing then; The ampoule that soldering and sealing is good is heated to the scope that temperature surpasses above 5-10 ℃ of bismuth chalkogenide liquefaction temperature Tliq, temperature along ampule length is controlled at ± 0.5 ℃ of scope in, and continue the enough time, make the constituent materials fusing, and be reacted into the chalkogenide of bismuth, in view of the above, during heating stir ampoule, evenly mixed to guarantee constituent materials; Material is chilled to room temperature with controlled speed, forms the chalkogenide homogeneous polycrystalline of bismuth; The chalkogenide polycrystalline of bismuth is positioned to the seed crystal of surface contact specific lattice structure; Seed crystal and bismuth chalkogenide polycrystalline are heated to the scope of following 30-40 ℃ of bismuth chalkogenide liquefaction temperature; To be heated to the scope of above 0-15 ℃ of bismuth chalkogenide liquefaction temperature near the bismuth chalkogenide polycrystalline of seed crystal; Should distinguish along bismuth chalkogenide polycrystalline length direction and move, form highly flawless bismuth chalkogenide single crystal whereby with 2-10mm/h speed; Bismuth chalkogenide monocrystalline is chilled to room temperature with controlled speed.
Another aspect of the present invention, the crystalline material that provides height layer to press from both sides, wherein every mole of described layer folder material can hold 3-10 mole object in the Fan Dewaersi groove, and there is no obvious lattice distortion.Object is selected from I A family and II A family metal.The further feature of this layer folder material is that △ G wherein is basic and object concentration is irrelevant.The chemical formula of layer folder material is G
zMe
yCh
z, wherein G is selected from I A family and II A family metal, and Me is selected from Bi and Sb, and Ch is selected from Te, Se and S, the scope of X is 3-10, and Y is 1 or 2, and the scope of Z is 1-3.
The loading position in the Fan Dewaersi groove in the used crystalline network of the present invention is shown in Fig. 1 letter.
The sectional view of the used district of preparation monocrystalline of the present invention fusing device is shown in Fig. 2 letter.
Fig. 3 is the discharge curve with the made battery of crystalline material of the present invention.
Distinguishing characteristics of the present invention is: have the height zero defect layered crystal material of suitable Impurity Distribution, it can press from both sides load object thing in the Fan Dewaersi of material groove by height layer.
Structure
Highly flawless chemical formula is Bi
yCh
zCompound family differentiated that wherein Ch is Te, Se and S, Y are 1 or 2 and the scope of Z is 1-3, it can allow very high object thing weight bearing power, except that the conventional weight bearing power of being scheduled to by the crystalline crystalline network, also has the pattern of lattice gas.The sosoloid of these compounds, i.e. Bi
2(Te
1-xSe
x)
3Also within the scope of the invention.Importantly both obtained high load, and do not had obvious lattice distortion, and the △ G of material does not have obvious relation with layer folder substrate concentration.When crystalline material cut down the cathode material element of Buddhist nun's battery as coffee, △ G was then relevant with the serviceability of this crystalline material.
Relate to the bismuth chalkogenide though discuss, can expect, as long as any stratified material has necessary lattice parameter, object weight bearing power and thermodynamic property are all within the scope of the invention.
Know that bismuth chalkogenide family comes crystalline with rhombohedron and hexagonal lattice.Six sides and rhombohedron lattice have the position of two types favourable acceptance, and they allow at Fan Dewaersi groove internal loading object thing.The basic point of these arguments is listed in the application of awaiting the reply jointly, and USSN is 07/784525, also is the application's part continuation application, herein in conjunction with reference.
The object position that Fig. 1 brief description is two types.First location 22 is positioned on the face of ditch groove center, and all the other positions 24, load object thing then is positioned at the wall 26 along groove.Groove is expected to be 3 to the total load head of object.When folder beginning layer plants oneself 22 to 24 more more smooth.Yet relative energy level can changing in layer clip process.The energy of all positions is approaching especially, to such an extent as to the position of object from a position " jump " to another different-energy is possible.The character of object thing resembles " lattice gas ".
Therefore, as if normal mode hints: the object load upper limit of no lattice distortion is 3.Yet we find that higher load is possible.With regard to the lattice types of Fig. 1 regulation, the interaction of the Fan Dewaersi groove inner orbit after the filling can cause the interaction that strengthens between object and object, and reduces object and the interatomic mean distance of object.From occupying load energy minimum position to free movement in whole Fan Dewaersi groove, this conversion just equals phase transformation.Lattice gas is condensed into the high-density attitude, it is defined as " semi liquid state " herein.
Because new have mean distance between smaller atom mutually, then can introduce extra object and distorted lattice not.Therefore, weight bearing power is 3 no longer to be the restriction of system, and fast, the object load of higher degree can have been accomplished now.The weight bearing power of having observed lithium in the bismuth chalkogenide of the present invention is until 8 and 9.We estimate in this class system weight bearing power even can also be higher, can think that especially this ability might be up to 10.
This compounds of the present invention has six stable sides or rhombohedron symmetry crystalline phase, be prepared into the defect concentration minimum to it so long, and Impurity Distribution is suitable.Prior art is known, Bi
2Ch
3The crystallizable one-tenth of the compound of class contains 5 atoms, and spacer is D
5 3d(R3m, a
O=9.83
, α=24.4 ° are for bismuth selenide) the rhombohedron structure cell.This crystalline structure is formed by waiting homoatomic to arrange each layer that is become with hexagonal lattice.Learn also that by prior art the hexagonal cells of bismuth selenide is also identified (a
O=4.14
, c
O=28.55
).
In battery, the △ G of discharge curve and cathode material (bismuth chalkogenide) is directly related.When the combination of object/main body is assessed, must be so consider the following thermodynamical coordinate relevant with △ G: the atom distribution entropy of main body/object, visitor-object and-interaction energy of visitor-main body, Fermi can variation (△ F), and lattice distortion (L
D).
Lattice gas in the system is condensed into semiliquid, can prevent tangible lattice distortion.In the case, layer folder surpasses 0 to 8 or the load of 9 scopes, the distortion that only produces the 2-3% scope.The Gibbs free energy of this not remarkably influenced of distortion system.Otherwise, at the TiS of existing layer folder lithium
2In, layer folder Li
xTiS
2The c-axle, promptly perpendicular to the axle of layer folder Fan Dewaersi groove, just presented with the little like that layer folder of X=0 to X=1 and to have increased by 10%.The variation of entropy (△ S) the only initial stage at layer clip process is just obvious.Therefore, in whole process, △ S is very little, and need not in the Gibbs free energy formula to consider.
Yet the characteristic of lattice has a significant impact all the other two thermodynamical coordinates.Interaction energy E
IntBeing that visitor-object and visitor-main body are interactional measures.The two receives the influence of properties of crystal lattice greatly.If lattice contains the defective and/or the dislocation of significance degree, enough uneven defect distribution is perhaps arranged, then relevant with limitation position least energy will be disperseed, and is just inhomogeneous along the filling of trench length direction.The size of crystal Fermi energy also is subjected to vacancy, the influence of lattice impurity position (lattice site impurities) and crystalline network.Aspect the crystalline impurities of differentiating permission, defective or profile of impurities are extremely important.If all defect accumulates near the Fan Dewaersi channel inlet, then object can not enter, even if the lattice purity is very high, weight bearing power also is low.Therefore, obviously, prepare the laminated crystalline material of the high load of the present invention's energy, careful growing crystal is important unusually.
Technology
Crystal growth technique of the present invention is described in detail in detail below, and with the highly flawless layered crystal material of preparation the present invention, this material has the specific properties of crystal lattice such as defect distribution.These detailed descriptions are at bismuth chalkogenide class, but should remark additionally, any layered crystal material, as long as it has necessary lattice parameter, object weight bearing power and thermodynamic property are all within the scope of the invention.
With high-purity (99.9999% is pure) bismuth of stoichiometric quantity and the chalcogen quartz ampoule bottle of packing into.In case of necessity, can be before use with each raw material elder generation zone-melting and refining.Depart from stoichiometric quantity, can produce n type or the adulterated material of p type, crystalline network and correlated performance can degenerate by occurrence features thereupon.Ampoule is evacuated to 10
-7MmHg, with small amounts of inert gas such as argon gas, or reducing gas such as hydrogen (3-10 circulation) recharge to pressure be 10
-3MmHg is afterwards with it soldering and sealing.Preferred especially hydrogen can be in growth technique reacts with oxygen because of it and to stop oxidation, and reduces because of the chalcogen fractional condensation of its vapor pressure due to reducing.
In first processing step, preparation earlier is polycrystalline material highly uniformly.Ampoule soldering and sealing is good in room temperature places stove, is heated above the temperature of 5-10 ℃ of its liquefaction temperature.Translational speed, temperature and reaction times can be selected at final compound.The table I is listed preparation polycrystalline Bi
2S
3, Bi
2Se
3And Bi
2Te
3Reaction conditions.Furnace temperature along the ampoule total length should be controlled at ± 0.5 ℃ within.Careful and accurate controlled temperature is very important, and this is because chalcogen volatility height.Can cause the chalcogen fractional condensation and depart from stoichiometric quantity along the temperature variation on the ampule length.For making temperature control optimizing, can use long body of heater along ampule length.The boosting coil can be used in two ends at stove, to reduce the temperature ladder in body of heater exit.
The processing condition of table I polycrystalline material
Processing condition Bi
2Te
3Bi
2Se
3Bi
2S
3
To the rate of heating of liquefaction temperature Tliq (℃/h) 30 20 15
Soaking time (h) 10 15 20 in the time of Tliq+10 ℃
Speed of cooling (℃/h) 50 40 35
In last hour in reaction times, stir or the vibration ampoule, to guarantee each component thorough mixing in the ampoule.The vibration of ampoule is preferably in the scope of 25-100Hz, and an end of bottle is fixed on the oscillation source carries out.Any conventional vibration device all can be the present invention and adopts.After reacting completely, with ampoule with the cooling of control speed slowly.
In case obtain homogeneous polycrystalline material, can be processed into highly flawless bismuth chalkogenide monocrystalline.Available any known method for monocrystal growth, such as descent method, pulling method and zone melting method (recrystallize).Zone melting method particularly, it is the most effective to obtaining high-purity monocrystalline.
Referring to Fig. 2, in the quartz boat 40 that includes required crystalline network seed crystal 42, distinguish molten.
Now advise that cleaning is 100 grades in the holding chamber.Seed crystal should be directed in the boat, so that each crystal layer 43 is horizontal.Whole device should be able to antidetonation, with isolated external vibration.Polycrystalline material blank 44 will be positioned to make its surface contact seed crystal.
Crystal growing furnace comprises two portions, promptly outer crystal growing furnace 46 and narrow district 47, and the former is used for keeping the high temperature on the whole length direction of blank, and the latter can move on arrow 48 directions, with the polycrystalline material of heating small portion.For the purpose of the preparation hexagonal structure, outer crystal growing furnace 46 keeps below the temperature of 35 ℃ of fusing points, and narrow district 47, only 2-3cm is long, then keeps the temperature that is higher than 10 ℃ of polycrystalline material fusing points.Different with first processing step of preparation polycrystalline material, in this step, blank is raised to operating temperature rapidly.Narrow district is placed in seed crystal/blank at the interface at first, and this zone is heated to material melting point.Narrow district 47 slowly moves down along the blank length direction then.Narrow district translational speed assigns to select according to particular group, and the speed of recommendation and other processing parameters are listed in the table II.Narrow district translational speed is an important technical parameters.If excessive velocities, then crystallization not exclusively and form defective.If speed is low excessively, then produce layer distortion, the bottom of the thermal treatment blank of the company's of touching quartz boat preferably is removed before the use.The monocrystal material of this prepared has and is lower than 10
12/ cm
3Defect concentration and be inversely proportional to the Impurity Distribution that direction is desired layer to press from both sides by institute.This monocrystalline contains 10 usually
6Layer/mm, and the lamellar spacing is 3-4
The grow processing condition of six side's monocrystalline of table II
Processing condition Bi
2Te
3Bi
2Se
3Bi
2S
3
Mp-35 ℃ Mp-35 ℃ Mp-35 ℃ of blank temperature
℃ Mp+ ℃ of narrow district temperature Mp+10 ℃ Mp+10
Narrow district translational speed 8mm/h 6mm/h 3mm/h
35 ℃/h of 40 ℃/h of 50 ℃/h of speed of cooling
Above-mentioned technology is improved a little and can be prepared the rhombohedron structure crystal, wherein, can use the rhombohedron seed crystal in district's process of smelting.In addition, in order to prepare the rhombohedron crystal, furnace temperature remains on following 30 ℃ of polycrystalline material fusing point, and narrow district then keeps melting temperature.
According to material component, can carry out preferably six sides or rhombohedron crystalline network.These all indignant drawing together are below shown in the III.
The preferred crystalline network of table III bismuth chalkogenide
Crystalline network BiSe
3Bi
2Se
3Bi
2S
3
Rhombohedron---
Six side X X-
Above-mentioned technology can provide highly flawless monocrystal material.Crystal further can be ground into particle and be used for element, every this particle all is a monocrystalline.Grinding technique will be selected to such an extent that many defectives and dislocation are not introduced crystal.Yet because the faint property of Vander Waals attraction, crystal is easily rived along trench length, and does not have too many lattice distortion danger.
In case make this material, be about to it and test as the active material of cathode Galvanic cell of packing into.The use of high-rise folder crystalline material in storage battery is disclosed in title and is " energy storing system ", on the same day in Shen Qing the U. S. application that awaits the reply jointly.A kind of standard element lithium anode, anhydrous LiClO
4Electrolytic solution, as negative electrode wait manufacture experimently.Faraday's electronics mole number to the external circuit of flowing through during the layer folder is monitored, and measures the lithium quantity of introducing the Van der Waals layer in this way.The typical discharge curve 50 that records with the bismuth chalkogenide negative electrode by the present invention's preparation shows as Fig. 3.Qualified crystalline material, every mole of bismuth chalkogenide of ergosphere folder at least 3 mole of lithium, and its discharge curve substantially flat, also, when layer folder limit of power was the 0.4-8 mole of lithium, the variation that observes was not more than 0.1-0.3V.The flatness of curve shows that the variation of Gibbs free energy is irrelevant with object concentration basically.
Lattice gas is condensed into semi liquid state itself and manifests the sudden change of discharge curve sparking voltage.Yet the actual change of voltage is very little, and the work of battery is had no effect.Fig. 3 shows bright smooth, slick discharge curve.In the object load is about 3 curve amplifier section 52, can observe " the point folding " of curve.This just can see under careful control condition.
In case as mentioned above, make height defect free crystal material, just can carry out layer folder, to obtain high-rise folder crystalline material of the present invention it.The available ordinary method of layer folder is carried out, for example crystalline material is exposed in the vapor phase of layer folder thing, perhaps crystalline material is placed a liquid that contains layer folder thing, perhaps allow the electric current electrochemical cell of flowing through, in this battery, this crystalline material is the electroactive material in one of them electrode.Preferably obtaining the method for high-rise folder thing load, is electrochemical method.
Claims (37)
1, a kind of lamellar single crystal material, wherein said material has enough low defect concentration and suitable Impurity Distribution, the two can allow every mole of said material in conjunction with foot, and the lithium of 3 moles on layer folder is in the Fan Dewaersi groove and do not have an obvious lattice distortion at least, and the further feature of said material is that △ G presss from both sides concentration with the lithium layer basically and has nothing to do.
2, a kind of chemical formula is Me
yCh
zThe lamellar single crystal material, wherein Me is selected from Bi and Sb, Ch is selected from Te, Se and S, Y are 1 or 2, Z is 1,2 or 3; Said material has enough low defect concentration and suitable Impurity Distribution, the two can allow in its Fan Dewaersi groove every mole of said material layer folder 3 mole of lithium and do not have obvious lattice distortion at least in conjunction with foot, and the further feature of said material is that △ G is irrelevant with lithium layer folder concentration basically.
3, a kind of chemical formula is Me
yCh
zThe lamellar single crystal material, wherein Me is selected from Bi and Sb, Ch is selected from Te, Se and S, Y are 1 or 2, Z is 1-3; Said material has enough low defect concentration and suitable Impurity Distribution, and the two can allow in its Fan Dewaersi groove every mole of said material layer to press from both sides 3 mole of lithium and do not have obvious lattice distortion at least in conjunction with foot; The voltage change that said material has as the discharge curve of the electrochemical cell of negative electrode is no more than 0.3V in the interlayer ability is the entire area of 0.4-8.
4, according to the monocrystal material of claim 1-3, wherein said material has hexagonal lattice structure, and defect concentration is not more than 10
12/ cm
3, the interlayer direction of Impurity Distribution gradient and lithium is inversely proportional in the Fan Dewaersi groove.
According to the monocrystal material of claim 1-3, it is characterized in that 5, the cohesion of lithium lattice gas occurs in weight bearing power and is approximately 3 parts.
6, according to claim 2,3 monocrystal material, wherein said material comprises Me
yCh
zSosoloid, wherein Me is selected from Bi and Sb, Ch is selected from Te, Se and S, Y are 1 or 2, Z is 1,2 or 3.
7, according to the monocrystal material of claim 1-3, wherein said material is ground into powder, and each powder all comprises single crystal.
8, according to the monocrystal material of claim 4, wherein said cohesion is the lattice gaseous state change semi liquid state from lithium.
9, a kind of battery that comprises claim 1-3 monocrystal material.
10, a kind of electrical condenser that comprises claim 1-3 monocrystal material.
11, a kind of thermoelectric element that comprises claim 1-3 monocrystal material.
12, a kind of method for preparing the high purity bismuth chalkogenide, it step that comprises is as follows:
In ampoule, pack into the sulfur family element and the bismuth of stoichiometric quantity;
The atmosphere that a kind of selection is provided to ampoule is with anti-oxidation;
The sealing ampoule;
The ampoule of sealing is heated to above 5-10 ℃ of bismuth chalkogenide liquefaction temperature Tliq, said temperature is being controlled on the ampoule total length ± 0.5 ℃ of scope in, and competent soaking time arranged, make each constituent materials fusing and reaction, generate required bismuth chalkogenide, stir ampoule between heating period, to guarantee each constituent materials uniform mixing;
With this material with the controlled speed cool to room temperature, to form the even polycrystalline of bismuth chalkogenide;
Place bismuth chalkogenide polycrystalline, make the seed crystal of its surface contact specific lattice structure;
Seed crystal and bismuth chalkogenide polycrystalline are heated to the temperature of the following 30-40 of bismuth chalkogenide liquefaction temperature Tliq ℃ scope;
To be heated to the temperature of about 5-15 ℃ of scope more than the bismuth chalkogenide Tliq near the narrow district of bismuth chalkogenide polycrystalline of seed crystal;
Move said narrow district along bismuth chalkogenide length direction with the speed of 2-10mm/h scope, thereby make height zero defect monocrystalline;
With said controlled speed of cooling the bismuth sulphide monocrystalline is as cold as room temperature.
13, according to the method for claim 12, wherein said bismuth chalkogenide monocrystalline has hexagonal lattice structure, and defect concentration is lower than 10
12/ cm
3, and interior impurity defect distribution gradient and the lithium layer folder direction of Fan Dewaersi groove is inversely proportional to.
14, according to the method for claim 12, wherein said selection atmosphere is argon gas.
15, according to the method for claim 12, wherein said selection atmosphere is hydrogen.
16, according to the method for claim 12, the purity of wherein said bismuth and sulfur family element is 99.9999%.
17, according to the method for claim 12, wherein said narrow sector width scope is 2-5cm.
18, according to the method for claim 12, wherein said stirring comprises vibration.
19, according to the method for claim 12, wherein said stirring comprises from a point of fixity vibration.
20, according to the method for claim 19, wherein the range of frequency of said vibration is 25-100Hz.
21, according to the method for claim 12, wherein said the stirring in last hour of heating carried out.
22, according to the method for claim 12, wherein Kong Zhi speed of cooling scope is 30-50 ℃/h.
23, according to the method for claim 12, above 10 ℃ of the Tliq that wherein said Heating temperature is the bismuth chalkogenide.
24, according to the method for claim 12, wherein said sulfur family element is a tellurium, and 10h is carried out in the ampoule heating of said soldering and sealing, and said controlled speed of cooling is 50 ℃/h, and said narrow district translational speed is 8mm/h.
25, according to the method for claim 12, wherein sulfur family element is a selenium, and to said soldering and sealing ampoule heating 15h, the speed of cooling of said control is 40 ℃/h, and said narrow district translational speed is 6mm/h.
26, according to the method for claim 12, wherein sulfur family element is a sulphur, heats said soldering and sealing ampoule 20h, and the speed of cooling of said control is 35 ℃/h, said narrow district translational speed 3mm/h.
27, according to the method for claim 12, wherein said seed crystal and said bismuth chalcogenide materialization thing polycrystalline are heated to below the Tliq 35 ℃, said narrow district temperature is above 10 ℃ of Tliq, this is at hexagonal structure.
28, according to the method for claim 12, during at the rhombohedron structure, said seed crystal and said bismuth chalkogenide polycrystalline are heated to following 30 ℃ of Tliq, and said narrow district temperature is Tliq.
29, a kind of electrical condenser, the bismuth chalkogenide that it comprises prepares by claim 12 method.
30, a kind of thermoelectric element, the bismuth chalkogenide that it comprises prepares by claim 12 method.
31, a kind of height zero defect monocrystal material by the preparation of claim 12 method.
32, a kind of layer of folder crystalline material, be included in the interior every mole of said layer of its Fan Dewaersi groove and press from both sides the object that material has the 3-10 molar range at least, said object is selected from I A and II A family metal, and the further feature of said layer folder material is that its △ G is irrelevant with object concentration basically.
33, a kind of chemical formula is G
xBi
yCh
zLayer folder crystalline material, wherein G is selected from I A and II A family metal, Ch is selected from Te, Se and S, the scope of x is 3-10, y is 1,2 or 3, the z scope is 1-3, and does not have obvious lattice distortion, said material another feature is that it is irrelevant with lithium layer folder concentration basically.
34, according to claim 32,33 layer folder crystalline material, wherein said layer folder thing is a lithium.
35, a kind of energy storing system that comprises claim 32 or 33 layers of folder crystalline material.
36, a kind of electrical condenser that comprises claim 32 or 33 layers of folder crystalline material.
37, a kind of thermoelectric element that comprises claim 32 or 33 layers of folder crystalline material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78452591A | 1991-10-29 | 1991-10-29 | |
| US784,525 | 1991-10-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1074249A true CN1074249A (en) | 1993-07-14 |
Family
ID=25132700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92113391A Pending CN1074249A (en) | 1991-10-29 | 1992-10-29 | The layered crystal material of energy load a large amount object |
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| Country | Link |
|---|---|
| EP (1) | EP0662251A1 (en) |
| JP (1) | JPH07505246A (en) |
| CN (1) | CN1074249A (en) |
| AU (1) | AU3176693A (en) |
| CA (1) | CA2122369A1 (en) |
| IL (1) | IL103583A0 (en) |
| RU (1) | RU94039535A (en) |
| WO (1) | WO1993008981A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419130C (en) * | 2004-11-03 | 2008-09-17 | 中国科学技术大学 | Sb2Te3 monocrystalline nanometer line ordered array and its preparation method |
| CN102822090A (en) * | 2010-03-31 | 2012-12-12 | 三星电子株式会社 | Thermoelectric material, and thermoelectric module and thermoelectric device including thermoelectric material |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4439660B2 (en) * | 2000-03-06 | 2010-03-24 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery |
| KR101695540B1 (en) | 2015-04-14 | 2017-01-23 | 엘지전자 주식회사 | Thermoelectric materials, and thermoelectric element and thermoelectric module comprising the same |
| CN113363493A (en) * | 2021-06-25 | 2021-09-07 | 惠州亿纬锂能股份有限公司 | Single crystal ternary positive electrode material, preparation method and battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3877988A (en) * | 1973-03-21 | 1975-04-15 | Mallory & Co Inc P R | Lithium-metal telluride organic electrolyte cell |
-
1992
- 1992-10-29 AU AU31766/93A patent/AU3176693A/en not_active Abandoned
- 1992-10-29 WO PCT/US1992/009243 patent/WO1993008981A2/en not_active Application Discontinuation
- 1992-10-29 EP EP93900503A patent/EP0662251A1/en not_active Withdrawn
- 1992-10-29 CN CN92113391A patent/CN1074249A/en active Pending
- 1992-10-29 JP JP5508566A patent/JPH07505246A/en active Pending
- 1992-10-29 CA CA002122369A patent/CA2122369A1/en not_active Abandoned
- 1992-10-29 IL IL103583A patent/IL103583A0/en unknown
-
1994
- 1994-04-28 RU RU94039535/26A patent/RU94039535A/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419130C (en) * | 2004-11-03 | 2008-09-17 | 中国科学技术大学 | Sb2Te3 monocrystalline nanometer line ordered array and its preparation method |
| CN102822090A (en) * | 2010-03-31 | 2012-12-12 | 三星电子株式会社 | Thermoelectric material, and thermoelectric module and thermoelectric device including thermoelectric material |
| US8933318B2 (en) | 2010-03-31 | 2015-01-13 | Samsung Electronics Co., Ltd. | Thermoelectric material, and thermoelectric module and thermoelectric device including the thermoelectric material |
| CN102822090B (en) * | 2010-03-31 | 2015-11-25 | 三星电子株式会社 | Thermoelectric material and comprise electrothermal module and the thermoelectric device of this thermoelectric material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07505246A (en) | 1995-06-08 |
| WO1993008981A2 (en) | 1993-05-13 |
| IL103583A0 (en) | 1993-03-15 |
| CA2122369A1 (en) | 1993-05-13 |
| WO1993008981A3 (en) | 1993-06-10 |
| EP0662251A1 (en) | 1995-07-12 |
| RU94039535A (en) | 1996-04-27 |
| AU3176693A (en) | 1993-06-07 |
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