CN1414924A - Method and apparatus for producing lithium based cathodes - Google Patents

Method and apparatus for producing lithium based cathodes Download PDF

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CN1414924A
CN1414924A CN00817837A CN00817837A CN1414924A CN 1414924 A CN1414924 A CN 1414924A CN 00817837 A CN00817837 A CN 00817837A CN 00817837 A CN00817837 A CN 00817837A CN 1414924 A CN1414924 A CN 1414924A
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lithium
flow
air
steam
substrate
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CN1195681C (en
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L·G·约翰逊
A·埃比尔
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Johnson Research and Development Co Inc
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Johnson Research and Development Co Inc
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Priority claimed from US09/447,250 external-priority patent/US6582481B1/en
Priority claimed from US09/511,275 external-priority patent/US6511516B1/en
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0027—Mixed oxides or hydroxides containing one alkali metal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

A method of producing a layer of lithiated material is provided wherein a mixture of Li(acac) and Co (acac)3 is dissolved in solution. The solution is deposited upon a substrate by atomizing the solution, passing the atomized solution into a heated gas stream so as to vaporize the solution, and directing the vaporized solution onto a substrate.

Description

Produce the method and apparatus of lithium based cathodes
Technical field
Relate generally to hull cell of the present invention relates in particular to the production of the thin film lithium negative electrode of rechargeable lithium ion batteries.
Background technology
Now, conventional cylinder battery comprises toxic materials, for example cadmium, mercury, lead and acid electrolyte.As producing material, these pharmaceutical chemicalss are by government control or forbid at present, have limited their employings as battery component thus.Another problem relevant with these battery materials be, the size and the weight of the activeconstituents that is directly connected to wherein to be adopted by the energy of these battery storage and release.Large-sized battery, for example those that see in automobile produce a large amount of electric currents, but have low-down energy density (watt hr/liter) and specific energy (watt hr/gram).Like this, they need long recharge time, and this causes them can't implement for many purposes.
In order to adapt to for the needs of high-energy-density and specific energy more, battery industry has turned to lithium-base battery.The principal focal point of battery industry is liquid and polymer electrolytic liquid system.But because the unstable of electrolyte solvent, these systems exist the inherent safety problem.In addition, with respect to the active-energy stored material that is used for anode and cathode, the battery of these types has the inert material composition of relative height ratio, for example collector, dividing plate, substrate.In addition, their higher relatively internal resistances cause low volume ratio (watt/kilogram), and this causes them can't implement for many purposes.
Produced film lithium cell, this battery has the film of the stepped construction that begins from the inactive ceramic substrate that cathode current collector and negative electrode have been installed thereon.On negative electrode deposit solid state electrolyte, then at deposit anode on the ionogen and anode collector is installed on anode.Typically, on entire cell, apply protective coating.Such lithium cell at length is described in U.S. Pat 5569520 and US5597660, at this particularly in conjunction with their specification sheets.But arrange (003) that the lithium cathode material has lithium cell that contains of these batteries, and as shown in fig. 1, this has produced the high internal resistance of cell, causes big capacitance loss.
Produce hull cell by the active material of cathode that forms by chemical vapor deposition techniques.In the past, produce the chemical vapor deposition negative electrode in (in the scope of 1-100 torr) under the quite low pressure environment.The needs of this quite low pressure environment have increased production cost widely and because but restive this pressure environment has significantly reduced the feasibility of production commercial product.In addition, such chemical vapor deposition typically carries out in the following manner: heating precursor solution so that cause that this solution evaporation is a gas phase, it can for example flow that argon is carried away to deposition location by non-reactive gas like this.Thereby precursor solution is heated the long time cycle may be caused that solution decomposes and can not work.In addition, the transmission line that high temperature and lp system need to transport solution extensively heats, and to prevent the condensation of evaporating solns between heating location and deposition location, has further improved production cost and complicacy thus.
Recently, the annealing of finding to contain under proper condition the lithium cathode material in substrate causes having the battery of the performance of remarkable increase, because annealing causes the lithium-containing materials crystallization.This crystallization material has hexagon stratiform structure, wherein contains the oxygen layer that Li and Co ionic alternate planes closely wrapped up and separates.Have now found that, be deposited on the aluminium substrate and by LiCoO 700 ℃ of annealing crystallizationizations by magnetron sputtering 2Demonstrate highly preferred orientation or have the structure of common oxygen, cobalt, lithium, illustrate by (101) face among Fig. 2 perpendicular to the substrate orientation.Because the lithium plane parallel is arranged in sense of current, this orientation provides the high-lithium ion diffusion by negative electrode, is preferred therefore.Because therefore over-drastic heating the causing large volume strain energy that is parallel to bottom rigid basement surface orientation usually in annealing process is thought to have formed preferred orientation.When crystal formation, they are naturally along minimum energy strained direction growth, like this, anneal and the volumetric strain energy that causes thereof help in common direction crystal growth perpendicular to the lower base surface, and this still passes through the preferred orientation of crystalline ion diffusion.
Past, annealing temperature under 600 ℃, lithium material does not significantly change in microtexture, therefore the orientation of lithium keeps non-crystalline state, as the 143rd volume No. 10, B.Wang in Journal of The ElectrochemicalSociety, J.B.Bates, F.X.Hart, B.C.Sales, that is instructed in the article of R.A.Zuhr and J.D.Robertson " Characterization of Thin-FilmRechargeable Lithium Batteries With Lithium Cobalt Oxide Cathodes " is such.This non-crystalline state has limited the diffusion of lithium ion by oxygen and cobalt layer, has produced the high internal resistance of cell thus, causes big capacitance loss.
Therefore, be annealed to most effectively orientation, think that negative electrode must bond to rigid basement and is heated to the time cycle of keeping an elongated segment near 700 ℃ in order to contain the lithium cathode material.
The other problem relevant with the chemical vapor deposition of lithium base introduction relates to solvent, and these solvents are used for combining with precursor material, for example lithium, cobalt, magnesium, nickel or iron.Typically, these solvent phase are local unstable, at high temperature are easy to cause fire or blast.
Therefore, need a kind of production method of the negative electrode that adopts in the film lithium cell of high performance rechargeable, this method need not quite low pressure system, need not anticathode annealing, need not unsettled solvent.In view of the above, the present invention has mainly reached such requirement.
Summary of the invention
In a preferred form of the invention, produce LiCoO 2The method of layer comprises step: the lithium based sols is provided; With lithium based sols atomisation; Heated air stream; The lithium based sols of atomizing is brought in the gas stream after the heating so that lithium based sols mist is heated into steam condition; Deposit steam in substrate.
Brief description of drawings
Fig. 1 is the explanation along the lithiated intercalation compound of (003) planar orientation.
Fig. 2 is the explanation along the lithiated intercalation compound of preferred (101) planar orientation.
Fig. 3 illustrates the orthographic plan of the film lithium cell of the principle of the invention in a preferred embodiment.
Fig. 4 is the cross-sectional view along the film lithium cell of Fig. 3 of face 4-4 orientation.
Fig. 5 is the synoptic diagram of equipment that is used for the film lithium cell negative electrode of deposit Fig. 3.
Fig. 6 shows that method according to preferred embodiment is deposited on the photomechanical printing figure of photo of the first area of cathode layer.
Fig. 7 shows that method according to preferred embodiment is deposited on the photomechanical printing figure of photo of the second area of cathode layer.
Fig. 8 shows that method according to preferred embodiment is deposited on the photomechanical printing figure of photo in the 3rd zone of cathode layer.
Fig. 9 is the photomechanical printing figure that is presented at after the annealing according to the photo of the first area of the cathode layer of the method deposit of preferred embodiment.
Figure 10 is the photomechanical printing figure that is presented at after the annealing according to the photo of the second area of the cathode layer of the method deposit of preferred embodiment.
Figure 11 is the photomechanical printing figure that is presented at after the annealing according to the photo in the 3rd zone of the cathode layer of the method deposit of preferred embodiment.
Figure 12 is the graphic representation according to the X-ray diffraction figure of the cathode layer of the method deposit of preferred embodiment.
Figure 13 is after annealing, according to the graphic representation of the X-ray diffraction figure of the cathode layer of the method deposit of preferred embodiment.
Figure 14 is the synoptic diagram of equipment that is used for the film lithium cell negative electrode of deposit Fig. 3.
Figure 15 is the cross-sectional view of the nozzle of the equipment shown in Figure 14.
Figure 16 is the optionally photomechanical printing figure of the photo of the cathode layer of embodiment deposit of basis.
Figure 17 is used for the synoptic diagram of the equipment of deposit negative electrode in a further advantageous embodiment.
Describe in detail
With reference to the accompanying drawings, shown the chargeable film lithium cell unit 10 that produces according to the method that embodies the principle of the invention with preferred form.Battery unit 10 has and is clipped in two aluminium cathode current collectors 11 between the negative electrode 12.Negative electrode 12 is made of lithiated intercalation compound or lithium metal oxide, for example LiCoO 2, LiMgO 2, LiNiO 2Or LiFeO 2Each negative electrode 12 has the solid state electrolyte 13 that forms thereon.Preferably, ionogen 13 is by lithium phosphorus oxynitride Li xPO yN zConstitute.Successively, each ionogen 13 has deposit anode 14 thereon.In the time of in being used in lithium ion battery, for example lithium metal, zinc nitride or nitrogenize tin constitute the material that preferred anodes 14 is suitable for by silicon tin oxynitride SiTON or other.At last, the anode collector 16 that preferably is made of copper or nickel is contacted to encase cathode current collector 11, negative electrode 12, ionogen 13 and anode 14 basically with two electrodes 14.
The method of invention will adopt the vapor deposition device shown in Fig. 5.Equipment comprises the maintenance groove 20 that is connected with ultrasonic generator 21.Maintenance groove 20 has gas inlet 22 that is connected to air pump 23 and the delivery channel 24 that extends to the injection tube 25 that at one end has nozzle 27.Injection tube 25 links to each other with heating unit 28.The heater block 29 that nozzle 27 is placed towards adjacent nozzle 27 straight.
Battery unit 10 is preferably made in the following manner.With so-called (2,2,6,6-tetramethyl--3,5-heptadione) lithium or Li (C 11H 19O 2) and (iii) Co (C of so-called acetylacetone cobalt 5H 7O 2) 3Or Co (acac) 3Li (TMHD) mixture be dissolved in organic solvent for example in the mixture of diglyme, toluene and HTMHD, to be created on the solution that keeps in the groove 20.The conventional atomizer of ultrasonic generator 21 or other type produces the solution spray, and this solution spray has the liquid distribution of sizes between 5 to 20 microns, and the preferred liquid size is about 5 microns.Because be incorporated into the pressure of the forced air that keeps groove by gas inlet 22 from air pump 23, droplet is transported to injection tube 25 by delivery channel 24, the gas inlet air-flow is pressurized between the 1-2p.s.i.
Injection tube 25 is heated to about 200 ℃, makes through herein droplet vaporize.Then, this steam directly reaches in about 1.5 to the 2 inches substrate of nozzle-end.Heater block 29 by the bottom is heated to about 400 ℃ with substrate.When steam reach and Contact Heating after substrate the time, Li (THMD) and Co (acac) in the air around 3With O 2Reaction makes to form LiCoO on substrate surface 2The layer and row from the volatile organic gas product.Have been found that the layer LiCoO that finally obtains 2Form the crystal that has along the preferred orientation of (101) face, as shown in Figure 2.Then, for illuvium on its opposite side, can the base is inverted.
Following example only is for the purpose of description, is not the restriction to theme of the present invention.
Be prepared as follows solution: be 53ml at volume, comprise in the organic solvent of diglyme, toluene, HTMHD mixture and mix Li (TMHD) of 0.25g part and the Co (acac) of 0.5g 3Mixture contains the HTMHD of diglyme, 10ml toluene and the 3ml of 40ml.The key advantage that this solution provides is that it can be processed in air under the condition that does not have a strong impact on.Make atomized soln through 1/4 inch ID delivery channel 24 with 2 liters/minute speed, and in order to realize the evaporation fully of this mist, with this atomized soln by being heated to about 2 inches long injection tubes of 200 ℃.Resulting steam directly arrives from the about 1.5 inches SiO of nozzle 27 2In the substrate.
Resulting LiCoO 2The layer show have three with one heart, clearly the zone: have first area, center R1 dark green, glossy appearance; Round first area R1, second area R2 with dark green outward appearance; Around second area R2, have the 3rd region R 3 of light green outward appearance.Think that this heterogeneity is the injecting scheme that adopts owing in test.
Next with reference to figure 6-8, they have shown the SEM photo in first, second and the 3rd zone respectively.Fig. 6 and 8 shows, suitable smooth in the first and the 3rd zone of this layer has the very uniform particle diameter of about 100nm.This planeness and particle diameter provide special cathode construction, and this is to adopt conventional gas-phase deposition method can not obtain preceding.This layer does not demonstrate tangible crack and peels off.
As shown in figure 12, all trizonal X-ray diffraction figures demonstrate the weave construction of height on (101) face.Should be noted that and LiCoO 2Relevant peak value is sharp-pointed, and this shows that this has good degree of crystallinity mutually.Be further illustrated in about 22 ° and demonstrate wide peak value, estimate and amorphous SiO 2Substrate is relevant.
Then, at 650 ℃ to LiCoO 2The sample annealing of layer 30 minutes.Sample after sample before the annealing and the annealing relatively demonstrate very little difference.Fig. 9-11 demonstrates first, second and the 3rd zone of the sample after the annealing respectively.Should be noted that by Figure 12 and 13 relatively the crystallization structure that shows (101) face at it keeps very similar.Like this, annealing process does not provide tangible income for cathode layer.
Particularly importantly, after annealing process, the crack in sample, occurred, illustrated in the ultra-Right side of Fig. 9.The crack type of this cathode material is a problem, because this will cause the damage of negative electrode, may cause the invalid of battery, and the applicant is just attempting to avoid.
Therefore, should be understood that the finally feasible LiCoO of the present invention with peculiar (101) face crystalline growth 2Form.Yet this technology is not needing LiCoO 2Layer carries out realizing under the annealed condition this result, the growth of peculiar to realize (101) crystalline.Finally, this utilizes chemical vapor deposition to realize under the condition around.
In case cathode layer is finished, can provide the remainder of battery, for example ionogen 13, anode 14, anode collector 16.Ionogen and anode can provide in the mode of any routine, for example by sputtering method, chemical vapor deposition, discharge decomposition, laser ablation, ion beam evaporation or the like.
Should be appreciated that in order to realize the peculiar evaporation of droplet must regulate the length of injection tube 25, the flow velocity that passes through injection tube 25, all these variations of heating of injection tube, for example, the input of heat must be complementary with the boiling point of solvent through injection tube.Can be by any usual manner heating injection tube, for example microwave radiation, heating lamp, resistance coil etc.And any conventional device can be used to solution be hazed or atomize.The inventive method also comprises, with solution be injected into vaporific form, then make its through the heating zone in case before reaching substrate, flash to by heating unit 28 vaporific, as shown in Figure 5.
It is also understood that in the methods of the invention and can adopt different lithiums and cobalt compound or chelate compound that preferably they can be lower than 300 ℃ of volatilizations.But, should be appreciated that the key advantage that described compound provides is and can handles in air.
At last, should be appreciated that the negative electrode of the preferred only first district R1 as battery.Believe the peculiar setting by a plurality of nozzles, first area R1 is optimizing dimensionally, and the second and the 3rd region R 2 and R3 minimizes even eliminate fully.
Then, the second method of producing the lithium layer with another preferred form of the present invention has been described with reference to figure 14-16.The inventive method adopts chemical vapor deposition device shown in Figure 14.Equipment 40 comprises the copper heated chamber 42 that wherein has heating unit 43, and preferred heating unit is by kuromore or other resistance heating coil that is suitable for platinum and be used for making at the hygrosensor 44 of heated chamber 42 detected temperatures for example.Heating unit 43 connects variable transformer 46, and this transformer control is applied to the power of resistance heating element 43, and is controlled at the heat in the heated chamber thus.Heated chamber 42 is fluidly got in touch by conduit 48 and pressure tank 47.Pressure tank 47 comprises for example supply of nitrogen and argon of rare gas element after the compression.Heated chamber 42 also interrelates with mobile mode and the supply that is included in the precursor solution in the non-reacted reservoir of for example being made by polyethylene 50 by conduit 51.Reservoir 50 comprises ultrasonic generator 52, and this producer nebulizes solution becomes according to top described mode.Reservoir 50 also interrelates with mobile mode and the supply of compressed inert in pressure tank 47 by conduit 55.Conduit 48 and 53 has variable valve 54, and its pilot-gas flows by each conduit.Nozzle 55 is connected with heated chamber 42, so that guide gas stream precursor the flowing on adjacent base 56 after the heating of carrying secretly.Preferably, nozzle is made by the pottery with about 1mm opening.As shown in Figure 15, nozzle 55 is connected with conduit 51 and has inner track, and this path is configured as reaching the effect of Venturi meter, and it helps from the precursor of conduit and the uniform mixing of gas stream that makes precursor and heating in the drawings.Substrate can also comprise hygrosensor, is used for the temperature of monitoring substrate during deposit.
Preferably, battery unit is made by the equipment of just having described 40 in the following manner.Open the variable valve 54 that is connected with conduit 48 and flow to heated chamber 42 from pressure tank 47 to allow rare gas element, wherein heating unit 43 will be increased to about 600 degrees centigrade through the temperature of the gas stream of heated chamber.Similarly, open the variable valve 54 of conduit 53, make the pressurized inert gas conduit 53 of flowing through enter in the reservoir 50.
Methyl ethyl diketone lithium and acetylacetone cobalt mixture (iii) are dissolved in the water solvent to generate solution, remain in the reservoir 50, driving by ultrasonic generator 52 makes its atomizing, also can be the conventional atomizer that can make a part of solubilisate mist formation of any other type.The precursor droplet that is produced by ultrasonic generator 52 is sent in the pre-warmed inert gas flow with the speed range of 5-50ml/hr.Owing to enter into the pressure of the pressurized inert gas of reservoir 50, the precursor droplet be carried to heated chamber nozzle 55 by conduit 51.
When heated chamber 42 downstreams that enter into heating unit 43, precursor droplet flash evapn is wherein with the gas stream of entrainment with steam to heating.The precursor droplet is by the reaction that contacts with the gas stream that heats in addition.This is used for chemically activating precursor and allows subsequently in suprabasil deposit.Then, by nozzle 55 this fluid is guided on the about 0.28 inch substrate of nozzle 55, wherein the precursor of gasification arrives substrate 56 and resolves into mixed oxide.Substrate 56 is heated to about 350 degrees centigrade.In this case, mixed oxide is a lithium cobalt oxide, and the deposition rate of lithium cobalt oxide is about 0.5 micron/hour.
Next with reference to Figure 15, the photomechanical printing figure of the final photo from the cobalt/cobalt oxide layer that generates by preceding method is shown on the aluminium ceramic bases.Employing contains the Co (acac) of the deionized water of 150ml, the Li of 0.09g (acac) and 0.3g 3Solution make this layer.Discharge rare gas element at 30psi from pressure tank 47, substrate 56 is heated to about 350 degrees centigrade.As shown in Figure 15, resulting layer comprises triangle/cone crystal, has reduced the preferably crystal growth form usually that layer annealed needed.
Next with reference to Figure 17, except pressure tank 47 not in the mobile mode with reservoir 50 is connected, show and the similar equipment shown in Figure 14.At this, only the pressure by Venturi meter makes precursor through conduit 51.
Should be appreciated that the similar equipment that can be designed as, it does not adopt Venturi nozzle, perhaps can adopt the sputter nozzle that droplet is transported to the heated chamber downstream of heating unit 43.
Should be appreciated that the term aqueous solution in this employing comprises it mainly being water base solution, can comprise other additive, for example organic solvent thus.It is also understood that the method just described can finish not having additionally to heat under the condition of substrate.
Therefore, provide a kind of height ratio capacity cell cathode as can be seen now, it is made under the condition of non-reactive gas not having under the environment of low-down pressure and do not have, but need not still to comprise good crystal arrangement under the condition of after annealing.Of course it is to be understood that under the condition of the essence of an invention in not breaking away from following claim, listed and scope, can carry out many modifications special preferred embodiment described here.

Claims (49)

1. method of producing the lithium intercalated material cathode layer of hull cell comprises step:
(a) provide the lithium based sols;
(b) with lithium based sols atomisation;
(c) heated air stream;
(d) the lithium based sols with atomizing is brought in the gas stream after preheating so that lithium based sols mist is heated into steam condition; And
(e) deposit steam in substrate.
2. according to the process of claim 1 wherein gas stream is made the chemical activation of lithium based sols with heat to a temperature.
3. according to the method for claim 1, further comprise the step (f) that heats substrate.
4. according to the process of claim 1 wherein that steam passes through the nozzle deposit.
5. according to the process of claim 1 wherein that described lithium based sols is lithium compound and the cobalt compound that is dissolved in the water solvent.
6. according to the method for claim 5, wherein said lithium compound is Li (acac).
7. according to the method for claim 5, wherein said cobalt compound is Co (acac) 3
8. according to the process of claim 1 wherein that mist has the droplets size distribution at 5 to 20 microns.
9. according to the process of claim 1 wherein that air-flow is made of rare gas element.
10. according to the method for claim 9, wherein inert gas flow comprises hydrogen.
11. according to the method for claim 9, wherein inert gas flow comprises argon gas.
12. a method of producing the lithium metal oxide layer comprises step:
(a) provide and have dissolved Li (acac) and Co (acac) in water solvent 3The solution of mixture;
(b) process solutions is vaporific to form;
(c) air-flow is gone into to preheat in this fog belt and be enough to make this fogization; And
(d) deposit steam in substrate.
13., further comprise the step (e) that heats substrate according to the method for claim 12.
14. according to the method for claim 13, wherein this mist has the droplets size distribution at 5 to 20 microns.
15. according to the method for claim 12, wherein air-flow is made of rare gas element.
16. according to the method for claim 15, wherein inert gas flow is a hydrogen.
17. according to the method for claim 15, wherein inert gas flow is an argon gas.
18. a method of producing the lithium metal oxide layer comprises step:
(a) provide solution with mixture of dissolved lithium base oxide and cobalt-based in solvent;
(b) process solutions is vaporific to form;
(c) air-flow is gone into to preheat in this fog belt and be enough to make this fogization; And
(d) deposit steam in substrate.
19. according to the method for claim 18, wherein said solvent is a water solvent.
20. according to the method for claim 18, wherein air-flow is made of rare gas element.
21. according to the method for claim 20, wherein rare gas element is a hydrogen.
22. according to the method for claim 20, wherein rare gas element is an argon gas.
23. according to the method for claim 20, wherein rare gas element is an argon gas.
24. a chemical vapor deposition device comprises:
Be used to produce the device of air-flow;
Be used to heat the heating unit of the air-flow that produces by generating unit;
Be used to keep the holding device of the supply of precursor solution;
Be used for precursor solution is transported to from described holding device the precursor delivery device of the airflow downstream of described heating unit, described air transporting arrangement comprises the atomisation unit that is used for the precursor solution atomisation; And
The air-flow that is used for containing the precursor solution after the heating is guided to suprabasil guide arrangement.
25. according to the equipment of claim 24, wherein said precursor delivery device comprises the gas under pressure supply of getting in touch with mobile mode and described holding device.
26. according to the equipment of claim 24, the described device that wherein is used to produce air-flow comprises the supply of pressurized inert gas.
27. a method of producing the lithium intercalated material cathode layer of hull cell comprises step:
(a) provide the lithium based sols;
(b) with lithium based sols atomisation;
(c) lithium based sols mist is heated to steam condition;
(e) deposit steam in substrate.
28., further comprise the step (e) that heats substrate according to the method for claim 27.
29. according to the method for claim 27, wherein steam is by the nozzle deposit.
30. according to the method for claim 29, wherein this mist is evaporating through before the nozzle.
31. according to the method for claim 29, wherein this mist evaporation after the process nozzle.
32. according to the method for claim 27, wherein said lithium based sols is lithium compound and the cobalt compound that is dissolved in the organic solvent.
33. according to the method for claim 32, wherein said lithium compound is Li (THMD).
34. according to the method for claim 32, wherein said cobalt compound is Co (THMD).
35. according to the method for claim 32, wherein organic solvent comprises diglyme.
36. according to the method for claim 32, wherein organic solvent comprises toluene.
37. according to the method for claim 32, wherein organic solvent comprises HTMHD.
38. according to the method for claim 32, wherein organic solvent is the mixture of diglyme, toluene and HTMHD.
39. according to the method for claim 27, wherein this thing has the liquid distribution of sizes at 5 to 20 microns.
40. a method that produces the lithium metal oxide layer comprises step:
(a) provide and have dissolved Li (TMHD) and Co (acac) in organic solvent 3Mixture solution;
(b) process solutions is vaporific to form;
(c) solution mist is heated into steam condition; And
(d) deposit steam in substrate.
41., also comprise the step (e) that heats substrate according to the method for claim 40.
42. according to the method for claim 40, wherein steam is by the nozzle deposit.
43. according to the method for claim 40, wherein this mist is evaporating through before the nozzle.
44. according to the method for claim 40, wherein this mist evaporation after the process nozzle.
45. according to the method for claim 40, wherein organic solvent comprises diglyme.
46. according to the method for claim 40, wherein organic solvent comprises toluene.
47. according to the method for claim 40, wherein organic solvent comprises HTMHD.
48. according to the method for claim 40, wherein organic solvent is the mixture of diglyme, toluene and HTMHD.
49. according to the method for claim 40, wherein this thing has the liquid distribution of sizes at 5 to 20 microns.
CNB008178372A 1999-11-23 2000-11-20 Method and apparatus for producing lithium based cathodes Expired - Fee Related CN1195681C (en)

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US09/447,250 US6582481B1 (en) 1999-11-23 1999-11-23 Method of producing lithium base cathodes
US09/511,275 US6511516B1 (en) 2000-02-23 2000-02-23 Method and apparatus for producing lithium based cathodes
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CN113913787A (en) * 2021-10-15 2022-01-11 浙江生波智能装备有限公司 Novel film preparation process and vacuum coating equipment

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Publication number Priority date Publication date Assignee Title
CN100511777C (en) * 2007-07-13 2009-07-08 张家港市国泰华荣化工新材料有限公司 A making method of cathode material for lithium ion battery
CN113913787A (en) * 2021-10-15 2022-01-11 浙江生波智能装备有限公司 Novel film preparation process and vacuum coating equipment

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