CN114335439A - Method for preparing high-crystallization thin film electrode and thin film battery through plasma induced growth - Google Patents
Method for preparing high-crystallization thin film electrode and thin film battery through plasma induced growth Download PDFInfo
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- CN114335439A CN114335439A CN202111650359.XA CN202111650359A CN114335439A CN 114335439 A CN114335439 A CN 114335439A CN 202111650359 A CN202111650359 A CN 202111650359A CN 114335439 A CN114335439 A CN 114335439A
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Abstract
The invention discloses a preparation method of a thin film electrode and a thin film battery with high crystallization degree through plasma induction growth. The preparation method of the invention avoids the problems of pollution, cracking, poor process compatibility, poor electrochemical performance and the like of the film substrate caused by film crystallization which is carried out by a high-temperature annealing treatment process in the prior art, breaks through the prior technical problems, obviously reduces the deposition temperature of the film electrode, and improves the low-temperature process compatibility of the battery; the working procedures and working hours of the thin film battery are shortened, resources are saved, and the cost is reduced; the solid/solid interface impedance of the battery is reduced, and the performance of the thin film battery is improved. The preparation method can prepare the high-crystallinity thin-film electrode and the thin-film battery with no pollution on the interface and uniform stress distribution.
Description
Technical Field
The invention belongs to the technical field of new energy devices, particularly relates to the field of solid-state batteries, and particularly relates to a plasma induced growth high-crystalline thin film electrode and a preparation method of a thin film battery.
Background
In recent years, lithium ion batteries having both high energy and high power density have attracted attention, and since most of lithium batteries are liquid systems and the liquid systems have great potential safety hazards, further development of lithium batteries has been long hindered, and a feasible approach to solving the problem of battery safety of the liquid systems is to perform solid-state and thin-film treatment on the batteries. The thin-film solid-state battery has the advantages of high safety coefficient, environmental friendliness, strong plasticity, adjustable thickness, capability of being prepared in batches by adopting a physical method and the like, and the high-energy density and flexible structural design of the thin-film solid-state battery has particularly prominent application prospect in the fields of military industry, medical treatment, aerospace, wearable electronic devices and the like.
At present, the preparation process of all-solid-state thin film batteries is still the main factor affecting the electrochemical performance and growth efficiency thereof, such as typical LiCoO2LiCoO synthesized at normal temperature and used in LiPON/Li all-solid-state thin-film battery system2The thin film is an amorphous structure with extremely low crystallinity, and the amorphous structure can be formed into a layered structure with better crystallinity only through a subsequent high-temperature annealing process, however, the high-temperature annealing process can cause the following problems: 1) the external high-temperature annealing treatment can not only cause the film substrate to be polluted, but also inevitably introduce larger internal stress into the film, so that a large number of micro cracks appear on the film and the micro short circuit condition is accompanied, which is not beneficial to lithium ion transmission, and the film has poorer electrochemical performance; 2) the annealing temperature in the high-temperature annealing process is generally over 600 ℃, and other functional materials, such as photoresist, a low-melting-point metal coating and the like, can be melted at the temperature, so that the process compatibility of the solid-state battery is extremely poor; 3) the CO in the air is inevitably contacted in the high-temperature annealing process2CO at high temperature2Carbonate insulators can be generated on the surface of the thin film, so that the interfacial resistance of the thin film is increased, and the electrochemical performance of the material is seriously influenced; 4) in the full-cell preparation process, the surface of the annealed film continuously grows electrolyte, and the interface delamination phenomenon can be generated due to stress mismatching.
At present, the growth of a thin film material with high crystallinity, low surface roughness and uniform interface stress at the temperature of less than 350 ℃ and even 200 ℃ is a technical problem to be broken through urgently in the field of solid-state batteries and a technical problem to be overcome urgently in the integrated preparation link of energy sources/devices.
Therefore, a thin film electrode with high crystallinity and a method for manufacturing the thin film battery, which can be manufactured at a relatively low temperature, are needed.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a thin film electrode and a thin film battery with high crystallinity through plasma induction, wherein the method adopts plasma induction to grow high crystallinity of a thin film material in the deposition process of the thin film battery, so as to prepare the thin film electrode with high crystallinity and the thin film battery with no pollution on the interface and uniform stress distribution.
In order to achieve the purpose, the invention adopts the following technical scheme: the preparation method comprises the steps of preparing the thin film electrode and the thin film battery by adopting a vacuum physical vapor deposition method, and simultaneously applying directional plasma flow to bombard a thin film material in the whole process to promote the high-crystallization growth of a current collecting layer, an electrode layer and an electrolyte layer of the thin film battery.
Preferably, the preparation method comprises the following steps:
s1: cleaning the substrate with plasma;
s2: sequentially depositing Ti and Pt current collector layers on the cleaned substrate under the induction of plasma;
s3: growing a thin film battery positive electrode on the current collecting layer by utilizing plasma induction;
s4: inducing the in-situ growth of a thin film battery electrolyte layer on the positive electrode of the thin film battery by using plasma;
s5: growing a thin film battery negative electrode on the electrolyte layer of the thin film battery in situ by utilizing plasma induction;
s6: and adding an encapsulation layer for the grown high-crystalline thin film battery.
Preferably, the plasma includes oxygen plasma, argon plasma and nitrogen plasma.
Preferably, the plasma is generated by applying a plasma bias drive, the plasma bias comprising: either or both of the dc bias and the rf bias are mixed.
Preferably, the voltage of the plasma bias is less than 100V and the power is less than 100W.
Preferably, the working temperature of the steps S2-S5 is between room temperature and 200 ℃.
Preferably, the thin film battery positive electrode and negative electrode materials are: any one of lithium cobaltate, lithium manganate, lithium iron phosphate, ferric fluoride, copper fluoride, vanadium pentoxide, lithium titanate and silicon.
Preferably, the material of the electrolyte has a lithium ion conductivity of more than 10-6S/cm, electron conductivity less than 10-9S/cm。
Preferably, the material of the electrolyte is any one of lithium phosphate, lithium aluminum titanium phosphate, lithium sulfide-phosphorus pentasulfide and lanthanum lithium zirconate.
Preferably, the whole process of the preparation method is suitable for the process of preparing the thin film electrode and the thin film battery by adopting any one method of a magnetron sputtering film deposition method, a laser film deposition method, a thermal evaporation film deposition method, an electron beam evaporation film deposition method and an ion beam sputtering film deposition method.
The invention has the beneficial effects that: the invention discloses a method for preparing a thin film electrode and a thin film battery with high crystallization through plasma induction growth, which firstly provides that in the preparation process of the thin film electrode and the thin film battery, the process of bombarding a thin film material by plasma to assist the thin film electrode and the high crystallization in-situ growth of electrolyte is added, the plasma can bombard the thin film material to promote the transition from an amorphous state to a high crystallization state at a low temperature lower than 200 ℃, the problems of pollution, cracking, poor process compatibility, poor electrochemical performance and the like of a thin film substrate caused by thin film crystallization which is required to be carried out through a high-temperature annealing treatment process in the prior art are avoided, and the prior technical problem is broken through; the working procedures and working hours of the thin film battery are shortened, resources are saved, and the cost is reduced; the solid/solid interface impedance of the battery is reduced, and the performance of the thin film battery is improved. The preparation method can prepare the high-crystallinity thin-film electrode and the thin-film battery with no pollution on the interface and uniform stress distribution.
Drawings
FIG. 1 is a schematic diagram of the principle of plasma-induced growth in an embodiment of the present invention;
FIG. 2 is a schematic diagram of a positive electrode of a plasma-induced thin film battery according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of an electrolyte for a plasma-induced growth thin film battery according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of a negative electrode of a plasma-induced growth thin film battery in an embodiment of the invention;
in the figure: 1. bias voltage input end 2, substrate tray and bias voltage cathode 3, substrate 4, atom or nano cluster 5, plasma 6, current collecting layer 7, thin film battery anode layer 8, thin film battery electrolyte layer 9 and thin film battery cathode layer.
Detailed Description
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
The invention is described in detail below with reference to the figures and specific embodiments.
A method for preparing a thin film electrode and a thin film battery with high crystallization by plasma induction growth is characterized in that when a vacuum physical vapor deposition thin film method is adopted to prepare the thin film battery electrode and the thin film battery, directional plasma flow is applied in the whole process to bombard thin film materials to grow the thin film battery electrode and an electrolyte layer with high crystallization, and the thin film battery electrode comprises a thin film battery positive electrode and a thin film battery negative electrode.
The preparation method comprises the following steps:
the first step is as follows: cleaning the substrate with plasma;
the second step is that: sequentially depositing Ti and Pt current collector layers on the cleaned substrate under the induction of plasma;
the third step: growing a positive electrode of the thin film battery on the fluid layer by utilizing plasma induction;
the fourth step: inducing the in-situ growth of a thin film battery electrolyte layer on the positive electrode of the thin film battery by using plasma;
the fifth step: growing a thin film battery negative electrode on the electrolyte layer of the thin film battery in situ by utilizing plasma induction;
and a sixth step: and adding an encapsulation layer for the grown high-crystalline thin film battery.
The whole process of the preparation method is suitable for the process of preparing the thin film battery electrode and the thin film battery by all vacuum physical vapor deposition thin film methods, wherein the vacuum physical vapor deposition thin film methods comprise a magnetron sputtering thin film deposition method, a laser thin film deposition method, a thermal evaporation thin film deposition method, an electron beam evaporation thin film deposition method and an ion beam sputtering thin film deposition method.
The plasma comprises oxygen plasma, argon plasma and nitrogen plasma, and when the thin film material is an oxide material, the oxygen plasma is selected; when the film material is a nitride material, selecting nitrogen plasma; when the thin film material is a metal material, an argon plasma is selected.
The plasma is generated by applying plasma bias voltage drive on the substrate layer, and the plasma bias voltage comprises: one or more of DC bias and RF bias, the plasma bias is selected as RF bias in chemical film deposition, the plasma bias is selected as DC bias in metal film deposition, the plasma bias is selected as the mixed bias of RF bias and DC bias in electrolyte film deposition, the voltage of the plasma bias is generally selected to be less than 100V, the power is selected to be less than 100W,
the selection standard of the positive electrode material of the thin film battery is to select a substance with higher reduction electrode potential, and the thickness of the substance is controlled between 1 and 10 mu m; the selection standard of the positive electrode material of the thin film battery is to select a substance with lower reduction electrode potential, and the thickness is controlled between 1 and 10 mu m; the electrolyte material is selected to be a material which does not chemically react with the positive and negative electrode materials and has a thickness of 1 to 2 μm. The thin film battery positive and negative electrode materials are therefore: any one of lithium cobaltate, lithium manganate, lithium iron phosphate, ferric fluoride, copper fluoride, vanadium pentoxide, lithium titanate and silicon;the material of the electrolyte is selected from materials with higher lithium ion conductivity and lower electron conductivity, and the lithium ion conductivity of the electrolyte is more than 10-6S/cm, electron conductivity less than 10-9S/cm, the electrolyte is generally selected from any one of lithium phosphate, lithium aluminum titanium phosphate, lithium sulfide-phosphorus pentasulfide and lanthanum lithium zirconate.
In the preparation process of the thin film electrode and the thin film battery, the plasma bombards the thin film at the low temperature of between room temperature and 200 ℃ for high crystallization, the bombardment process is accompanied with the whole period of thin film growth, wherein the plasma temperature is set at 200 ℃ in the growth process of the positive electrode of the thin film battery, and the plasma temperature is set at room temperature in the growth process of the electrolyte and the negative electrode.
The following describes the processes for preparing a thin film electrode and a thin film battery by using the method for depositing a thin film by magnetron sputtering as an example and by using the method for preparing a thin film electrode and a thin film battery by plasma induced growth disclosed by the invention in combination with fig. 1 to 4.
In a first step, the substrate 3 is cleaned. Ultrasonically cleaning the substrate 3 for 30min by using alcohol, drying, putting into a plasma cleaning machine, turning on a power supply, and vacuumizing to 0.1Pa by using a vacuum pump; then opening an air inlet valve, checking an air source reducing valve, and controlling the pressure to be 20 Pa; finally, turning on an RF power supply, and cleaning for 5-10min by using plasma until the substrate 3 is cleaned until no obvious trace or adhesive is left on the surface;
and secondly, adopting a radio frequency magnetron sputtering method, and carrying out low-temperature plasma induction assisted growth of a current collector layer, wherein the process is shown in the figure 1 and the figure 2. Loading 10-100V voltage on a bias input end 1, firstly, sputtering and depositing a metal Ti film by using high-purity metal Ti as a target material and high-purity Ar as sputtering gas under the conditions that the working air pressure is 0.1-0.5 Pa and the sputtering power is 200-600W; then, sputtering and depositing a metal Pt film by adopting a direct-current magnetron sputtering method and using high-purity metal Pt as a target material and high-purity Ar as sputtering gas under the conditions that the working air pressure is 0.1-0.5 Pa and the sputtering power is 50-300W; controlling the total thickness of the Ti and Pt films to be 0.5-2 mu m, finishing the preparation of a current collector film 6, wherein a substrate tray and a bias cathode 2 are positioned between a bias input end 1 and a substrate 3 in the figures 1 and 2, and a plasma 5 directionally bombards a current collector layer material in the figures, so as to induce atoms or nanoclusters 4 of the material to directionally grow, thereby obtaining the current collector layer.
And thirdly, adopting a radio frequency magnetron sputtering method, and carrying out low-temperature plasma induction assisted growth on the positive electrode layer of the thin film battery, as shown in figure 2. Loading 10-100V to bias input end 1 to obtain high purity LiCoO2Using argon-oxygen mixture as sputtering gas, working pressure is 0.3-3.0 Pa, Ar gas flow is kept at 80sccm, O2The gas flow is kept at 20sccm, the sputtering power is 200-800W, the substrate heating temperature is 200 ℃, and LiCoO is sputtered and deposited2Controlling the thickness of the film to be 0.2-2 mu m, and finishing the deposition of the anode film 7.
And fourthly, adopting a radio frequency magnetron sputtering method, and carrying out low-temperature plasma induction assisted growth on the electrolyte layer of the thin film battery, as shown in figure 3. The bias input terminal 1 is loaded with 10-100V to obtain high purity Li3PO4As target material, the sputtering gas is high-purity N2The working pressure is 0.5-3.0 Pa, the sputtering power is 500-900W, N2And keeping the gas flow at 100sccm, sputtering and depositing the LiPON film, and controlling the thickness to be 0.5-3 mu m to finish the deposition of the solid electrolyte film 8.
And fifthly, adopting a radio frequency magnetron sputtering method, and carrying out plasma induction assisted growth on the negative electrode layer of the thin film battery, as shown in figure 4. The bias input terminal 1 is loaded with 10-100V, high-purity metal or nonmetal (Sn, Si, etc.) or metal oxide (SnO, ZnO, TiO2, etc.) is used as a target material, argon or argon-oxygen mixed gas is used, the working pressure is 0.3-3.0 Pa, the flow rate of Ar gas is kept at 50-100 sccm, O is added2The gas flow is kept at 0-20 sccm, the sputtering power is 200-800W, and the thickness is controlled at 0.5-2 μm, so as to complete the deposition of the cathode film 9.
And finally, packaging the battery to finish the preparation of the thin film battery.
Claims (10)
1. The preparation method is characterized in that when the film electrode and the film battery are prepared by adopting a vacuum physical vapor deposition method, directional plasma flow is applied in the whole process to bombard a film material to promote the high-crystal growth of a current collecting layer, an electrode layer and an electrolyte layer of the film battery.
2. The method for preparing a thin film electrode and a thin film battery with high crystallization degree by plasma induction growth according to claim 2, wherein the preparation method comprises the following steps:
s1: cleaning the substrate with plasma;
s2: sequentially depositing Ti and Pt current collector layers on the cleaned substrate under the induction of plasma;
s3: growing a thin film battery positive electrode on the current collecting layer by utilizing plasma induction;
s4: inducing the in-situ growth of a thin film battery electrolyte layer on the positive electrode of the thin film battery by using plasma;
s5: growing a thin film battery negative electrode on the electrolyte layer of the thin film battery in situ by utilizing plasma induction;
s6: and adding an encapsulation layer for the grown high-crystalline thin film battery.
3. The method for preparing a thin film electrode and a thin film battery with high crystallinity through plasma-induced growth according to claim 2, wherein the plasma comprises oxygen plasma, argon plasma and nitrogen plasma.
4. The method for preparing a thin film electrode and a thin film battery with high crystallization degree by plasma-induced growth according to claim 2, wherein the plasma is generated by applying a plasma bias voltage drive, and the plasma bias voltage comprises: either or both of the dc bias and the rf bias are mixed.
5. The method for preparing a thin film electrode and a thin film battery with high crystallization degree by plasma induction growth according to claim 4, wherein the voltage of the plasma bias is less than 100V, and the power is less than 100W.
6. The method as claimed in claim 2, wherein the operating temperature of steps S2-S5 is between room temperature and 200 ℃.
7. The method for preparing the thin film electrode and the thin film battery with high crystallization degree by plasma induction growth according to claim 2, wherein the materials of the positive electrode and the negative electrode of the thin film battery are as follows: any one of lithium cobaltate, lithium manganate, lithium iron phosphate, ferric fluoride, copper fluoride, vanadium pentoxide, lithium titanate and silicon.
8. The method for preparing a thin film electrode and a thin film battery with high crystallization degree by plasma induction according to claim 2, wherein the lithium ion conductivity in the material of the electrolyte is more than 10-6S/cm, electron conductivity less than 10-9S/cm。
9. The method for manufacturing a thin film electrode and a thin film battery having high crystallinity through plasma-induced growth according to claim 8, wherein the electrolyte is made of any one of lithium phosphate, lithium aluminum titanium phosphate, lithium sulfide-phosphorus pentasulfide, and lanthanum lithium zirconate.
10. The method for preparing a thin film electrode and a thin film battery with high crystallization degree by plasma induction according to claim 2, wherein the whole process of the preparation method is suitable for the process of preparing the thin film electrode and the thin film battery by adopting any one method of a magnetron sputtering film deposition method, a laser film deposition method, a thermal evaporation film deposition method, an electron beam evaporation film deposition method and an ion beam sputtering film deposition method.
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| CN102037586A (en) * | 2008-05-21 | 2011-04-27 | 应用材料股份有限公司 | Thin film batteries and methods for manufacturing same |
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