CN101771168B - Method for preparing miniature lithium battery - Google Patents

Method for preparing miniature lithium battery Download PDF

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CN101771168B
CN101771168B CN2010101116098A CN201010111609A CN101771168B CN 101771168 B CN101771168 B CN 101771168B CN 2010101116098 A CN2010101116098 A CN 2010101116098A CN 201010111609 A CN201010111609 A CN 201010111609A CN 101771168 B CN101771168 B CN 101771168B
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film
anode
cathode
photoresist
solid electrolyte
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CN101771168A (en
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董全峰
宋杰
郑明森
吴孙桃
吴启辉
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Xiamen University
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Xiamen University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a method for preparing a miniature lithium battery, relates to a lithium battery, and provides the method for preparing the miniature lithium battery, which is easy to implement and compatible with micro-processing technology. The miniature lithium battery consists of a substrate, a cathode current collector, a cathode film, a solid electrolyte film, an anode film, a lower-layer anode current collector and an upper-layer anode current collector. The method comprises the following steps of: depositing a layer of metal film on the substrate with a chemical deposition method or a physical deposition method serving as the cathode current collector and the lower-layer anode current collector; limiting a cathode graph on the cathode current collector with a photoresist, depositing a cathode thin film with the physical deposition method, removing the residual photoresist with an inert solvent stripping method to obtain the cathode thin film of the limited graph, and performing annealing treatment; limiting structures of the required solid electrolyte film and the anode film with the photoresist; limiting the structures of the solid electrolyte film and the anode film by using the photoresist as a sacrificial layer 4; preparing the solid electrolyte film, the anode film and the upper-layer anode current collector; and stripping the sacrificial layer to obtain the miniature lithium battery.

Description

The preparation method of miniature lithium battery
Technical field
The present invention relates to a kind of lithium battery, especially relate to a kind of preparation method who adopts the full-solid-state minisize lithium cell of micro-processing technology preparation.
Background technology
In recent years, along with microelectromechanical systems (MEMS) technology rapid development, as: the fast development that microsensor, little gyro and Space Facilities are microminiaturized, relevant with it miniature energy technology also obtains people's attention more and more.Usually adopting external power supply is microelectromechanical systems (MEMS) power supply, can produce some defectives: as, reduced the design efficiency of MEMS; The noise that wiring point electric capacity produces; ([1] Koeneman P B, Busch-Vishniac I J, Wood K L.Journal of.Microelectromechanacal System.1997,6 (4): 355-362) such as interactive interference of supply lines and holding wire.Therefore, realize the microminiaturization of the energy, the integrated major issue that has become the solution of being badly in need of among the development MEMS with the defective that overcomes external power supply.In addition, very lagre scale integrated circuit (VLSIC) (VLSI) also to power supply proposed similar requirement ([2] Minko B..SolarEnergy Materials&Solar Cells, 2000,62:21-35).
In order to reduce the noise of power supply; Reduce the consumption ease of electric energy in the dynamic random container (DRAMS) that high density is arranged; Require in the actual production power supply and electronic equipment are connected as a single entity; Realize the miniature localization of the energy, the minicell that promptly quality of match is light, energy is high, the life-span is long on metal-oxide semiconductor (CMOS) storage piece.In the world the research of little energy is mainly contained several types of micro zinc-nickel battery, miniature lithium battery, miniature solar battery, miniature thermoelectric cell and micro fuel cells etc. in recent years.
Full-solid-state minisize lithium cell occupies critical role because of its integrated preferably compatibility in all kinds of minicells, also be to realize MEMS, microminiaturized, the integrated better selection of the VLSI energy.
It mainly is cathodic coating, solid electrolyte film and anode film that the structure of full-solid-state minisize lithium cell is formed.Relating to structure aspects has a variety of reports, and common structure can be described referring to U.S. Pat 5338625.Can be through deposition cathode current collector, cathodic coating, solid electrolyte film, anode film, anode current collector constitute successively on certain substrate (like monocrystalline silicon piece).The structure of battery has a variety of reports, and common structure such as U.S. Pat 5338625 are described.
The thin-film material that preparation constitutes micro cell mainly adopts micro-processing technology, as: methods such as magnetron sputtering, pulsed laser deposition, vacuum thermal evaporation deposition.
Because the reduction of thickness, electrolyte just can be used the poor lithium ion conductor-inorganic solid electrolyte of some ionic conductivities, for example employing rf magnetron sputtering Li under nitrogen atmosphere such as the Bates of U.S. Oak Ridge National Laboratory 3PO 4The method of target has prepared Li 3.3PO 3.9N 0.17(LiPON) film, conductivity at room temperature reach 2.3 (± 0.7) * 10 -6S/cm, electrochemical stability window is 5.5V, and it has been prepared Li/LiPON/LiCoO as solid electrolyte 2And Li/LiPON/V 2O 5Deng all solid-state thin-film lithium battery ([3] Wang B, Bates J B, Hart F X et al.J.Electrochem.Soc.1996,143:3203-3213).
The use of the solid-state inorganic electrolyte of electrochemical stability has improved the oxidation-reduction stability of battery greatly, just can consider with the high cathode material of some oxidation activities.Because the Li of solid-state inorganic electrolyte +Ionic conductivity is low relatively, and the ratedeterming step of cell reaction possibly be that lithium ion is in electrolytical transmission course.So just do not have the very necessary electrode material that uses, increased the selection of electrode materials degree, make those amorphous state molybdenum of low lithium ion diffusion coefficient and sulfide and the oxide and the V of titanium arranged especially with respect to its crystal structure form with high-lithium ion diffusion 2O 5Film becomes possibility.Reported the solid-state thin-film battery of multiple system in the document, for example Li/LiPON/LiCoO 2, SiTON/LiPON/LiCoO 2, SnN x/ LiPON/LiCoO 2, Cu/LiPON/LiCoO 2And Li/LiPON/Li xMn 2-yO 4Etc. system ([4] Bates J B, Dudney N J, Neudecher B et al.Solid State Ionics, 2000,135:33-45; [5] Neudecher B J, Dudney N J, Bates J B.J.Electrochem.Soc., 2000,147:517-523; [6] Neudecher B J, Zuhr R A, Bates J B.J.Power Sources, 1999,81:27-32; [7] Dudney N J, Bates J B, Zuhr R A et al.J.Electrochem.Soc., 1999,146:2455-2464; [8] Hart F X, Bates J B.J.App.Phys., 1998,83:7560-7566).
Lithium anode film commonly used mainly is under the environment of high vacuum, to be deposited on the solid electrolyte with hot evaporation coating method.But in some integrated circuits (IC) manufacture craft, adopt reflow solder technique; In manufacturing process, IC is heated to 250~260 ℃ rapidly, because lithium has lower fusing point (180 ℃); Therefore when temperature surpasses 250 ℃, can lithium battery be destroyed because of the anode fusing.In addition,, react with airborne oxygen and water vapour etc. easily, therefore need a kind of anode material of miniature lithium ion battery of alternative metals lithium because lithium metal is very active.Research shows; Various metal oxides (for example tin-oxide and based on the composite oxides of tin) are anode material ([9] Neudecker of a kind of miniature lithium ion battery of fine alternative metals lithium; B.J., R.A.Zuhr, et al. (1999) .Journal of Power Sources 82:27-32); Its Heat stability is good, chemical property is more stable in air.The preparation method of metal-oxide film is easier, can be through a lot of methods magnetron sputtering for example, and thermal evaporation corresponding metal in oxygen atmosphere, the preparation of methods such as chemical vapour deposition (CVD).
In the technology of preparation battery, can use masks such as aluminium with special pattern, stainless steel to limit the shape of each component film of deposition micro cell; This mask technique is highly suitable for Centimeter Level or the more preparation of large scale battery; But rim effect can take place and can't obtain accurate figure in this mask method when preparation smaller szie micro cell; And there is pollution in mask in the deposit film process, also may scratch the film that has deposited and damages battery.Therefore, if micro cell will be applied on the various microdevices, its preparation technology must be compatible with microelectronics preparation technology.
Summary of the invention
The purpose of this invention is to provide a kind of easy realization, and with compatible miniature lithium battery of micro-processing technology and preparation method thereof.
Miniature lithium battery of the present invention is made up of substrate, cathode current collector, cathodic coating, solid electrolyte film, anode film, lower floor's anode collector and upper strata anode collector; Substrate is monocrystalline silicon, quartz, pottery or polymer flexibility substrate; Cathode current collector and lower floor's anode collector are prepared on the substrate; Cathodic coating is deposited on the cathode current collector, and solid electrolyte film covers on the cathodic coating, is separated by solid electrolyte film between cathodic coating and the anode film; And can the conductive lithium ion, said solid attitude electrolyte adopts LiPON or LiBO 2, anode film and upper strata anode collector are positioned on the solid electrolyte film.
Said cathodic coating can adopt the transition metal oxide cathodic coating.Said anode film can adopt the tin-oxide anode film.
The preparation method of miniature lithium battery according to the invention may further comprise the steps:
1) on substrate, deposits layer of metal film as cathode current collector and lower floor's anode collector through chemical deposition or physical deposition method;
2) on cathode current collector, limit cathode pattern with photoresist, adopt physical deposition method deposition cathode film then, the method for peeling off with atent solvent is again removed remaining photoresist, obtains limiting the cathode thin film of figure, again annealing in process;
3) limit the structure of required solid electrolyte film and anode film with photoresist; Make the structure that limits solid electrolyte film and anode film with photoresist as sacrifice layer 4;
4) preparation solid electrolyte film, anode film and upper strata anode collector;
5) adopt wet method or dry method to peel off sacrifice layer (photoresist) at last, obtain the miniature lithium ion battery of complete structure.
In step 1), the material of said metal film can be Pt, Au, Ni or Al etc., and said substrate can be monocrystalline silicon, quartz, pottery or polymer flexibility substrate etc.
In step 2) in, the area of said cathode pattern can be 0.1~1mm 2, the thickness of said cathode thin film can be 0.1~1 μ m, and said cathode thin film can adopt LiCoO 2Film, LiMn 2O 4Film or V 2O 5Films etc., the area of said cathode thin film can be 0.1~1mm 2, said annealing in process is preferably with cathode thin film 300~700 ℃ of annealing in process of warp in oxygen or air; Said physical deposition method can adopt methods such as magnetron sputtering or pulsed laser deposition; It is the photoresist of 5124E or AZ4620 that said photoresist can adopt existing product type.
In step 3), it is the photoresist of 5124E or AZ4620 that said photoresist can adopt existing product type.
In step 4), said solid electrolyte film can be selected LiPON film or LiBO for use 2Film, performance is a greater impact easily in the air because the LiPON film is exposed to, and subsequent technique can avoid electrolytic thin-membrane to be exposed in the air; Therefore said preparation solid electrolyte film, anode film and upper strata anode collector can adopt following method: according to the preparation method of cathode thin film, etch the electrolyte thin film pattern with photoresist earlier, then under the condition of not opening vacuum chamber; Method successive sedimentation LiPON film and anode film with magnetron sputtering; Deposit layer of metal again as the upper strata anode collector, said metal can adopt Pt, Au; Ni, Al or Cu etc.
Compare with prior art, the present invention has outstanding advantage and effect:
1) preparation method and microelectronics preparation technology are compatible, and product can be realized with microdevice integrated.
2) adopt the method for successive sedimentation to avoid solid electrolyte LiPON film to be exposed in the air.
3) in case miniature lithium battery form, can be by anode film, anode collector forms sealing to electrolyte and negative electrode, mobilely in air before miniature lithium battery uses like this reaches storage and can be effectively protected.
4) adopt metal oxide as anode material; Perhaps in the initial charge process, on anode collector, generate lithium metal as anode; Then can reduce the difficulty of technology, the inert environments that needs usually when avoiding the use of lithium metal and the requirement of high leakproofness as anode.
Description of drawings
Fig. 1 is the structural representation of embodiment of the invention substrate.
Fig. 2 has deposited the structural representation of cathodic metal collector and lower floor's anode collector for the embodiment of the invention.
Fig. 3 is deposited on the structural representation of the cathodic coating on the cathode current collector for the embodiment of the invention.
Fig. 4 is a structural representation of having photoresist before continuous sputter solid electrolyte of the embodiment of the invention and the anode film.
Fig. 5 is good solid electrolyte of the continuous sputter of the embodiment of the invention and anode film, the structural representation of anode collector layer.
Fig. 6 is the structural representation of the miniature lithium battery that discharges behind the embodiment of the invention stripping photoresist.
Electronic Speculum (SEM) photo of the miniature lithium battery product that Fig. 7 makes for the embodiment of the invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described further.
Shown in Fig. 1~7; Miniature lithium battery of the present invention is made up of substrate 1, cathode current collector 2a, cathodic coating 3, solid electrolyte film 5, anode film 6, the anode collector 2b of lower floor and upper strata anode collector 7; Substrate 1 is monocrystalline silicon, quartz, pottery or polymer flexibility substrate, and cathode current collector 2a and the anode collector 2b of lower floor are prepared on the substrate 1, and cathodic coating 3 is deposited on the cathode current collector 2a; Solid electrolyte film 5 covers on the cathodic coating 3; Separate by solid electrolyte film between cathodic coating 3 and the anode film 6, and can the conductive lithium ion, said solid attitude electrolyte adopts LiPON or LiBO 2, anode film 6 is positioned on the solid electrolyte film 5 with upper strata anode collector 7.
Said cathodic coating 3 can adopt the transition metal oxide cathodic coating.Said anode film 6 can adopt the tin-oxide anode film.
In Figure 4 and 5, mark 4 is sacrifice layer (adopting photoresist as sacrifice layer).
Below provide the concrete preparation method of said miniature lithium battery.
Embodiment 1
1) select substrate (structure is referring to Fig. 1) preparation cathode current collector and anode collector substrate 1 employing monocrystalline silicon substrate, adopt the dried wet oxygen method oxide layer of on substrate 1, growing, oxide layer is as insulating barrier, and thickness is about 500nm.The cathode current collector that photoetching is good required and the structure graph of anode collector; The method of using direct current sputtering then splash-proofing sputtering metal Ti layer (thickness 20nm) successively on the substrate 1 of the good required collector figure of photoetching; Metal Pt layer (thickness is 300nm); The metal Ti layer is as tack coat, and the metal Pt layer of deposition is as cathode current collector 2a and the anode collector 2b of lower floor (referring to Fig. 2).
2) LiCoO 2The preparation of cathodic coating
After the step 1), 5124E limits the cathode zone figure that needs the covered cathode film with photoresist on cathode current collector 2a, adopts the method deposition cathode film of rf magnetron sputtering then.Use diameter 100mmLiCoO 2Cavity air pressure is evacuated to 10~4Pa before the ceramic sputter targets, sputter, and sputtering atmosphere is the argon oxygen gas mixture, and volume ratio is Ar: O 2=3: 1, gas pressure is 1.3~3.0Pa, and sputtering power is 100W, and the temperature of substrate is a room temperature during deposition, and sedimentation time 1~2h can obtain LiCoO 2, cathodic coating 3 (referring to Fig. 3).Again with LiCoO 2 Cathodic coating 3 is heat-treated, at O 2In the atmosphere, rise to 600~700 ℃ with 5 ℃/min heating rate from room temperature, annealing in process 0.5~2h naturally cools to room temperature and takes out.Gained LiCoO 2The thickness of cathodic coating 3 is 200~400nm, and the area of cathode zone is 0.5 * 0.5mm 2
3) enclose photoresist before preparation solid electrolyte and the anode film
Step 2) after, limits the structure of required solid electrolyte film and anode film as sacrifice layer 4 (referring to Fig. 4) with the photoresist of model 5124E;
4) LiPON solid electrolyte film, SnO xThe preparation of anode film and anode collector
After the step 3, use the Li of diameter 100mm 3PO 4Ceramic sputter targets, it is high-purity N that the preceding cavity air pressure of sputter is evacuated to 10~4Pa sputtering atmosphere 2, air pressure 1.3Pa, sputtering power 100~200W, sputtering time 2h can obtain the LiPON dielectric film 5 (referring to Fig. 5) of deposit thickness 400nm.Under the situation of not opening vacuum chamber, adopt the method for direct current sputtering to carry out continuous sputter, can deposit and obtain SnO xAnode film 6 (referring to Fig. 5).Use the metal Sn sputtering target of diameter 100nm during preparation, sputtering atmosphere is Ar and O 2Gaseous mixture, volume ratio are Ar: O 2=2: 1, air pressure is 1.3Pa, sputtering power 50~200W, and sedimentation time is 10~60min, considers SnO xThe irreversible capacity loss of first charge-discharge, its deposit thickness should with cathodic coating LiCoO 2Film is complementary, and LiCoO2 is 10: 1~20: 1 with the thickness ratio of SnOx, and the method plated metal Ni layer that continues then to adopt direct current sputtering is as upper strata anode collector 7 (referring to Fig. 5), and thickness is 200nm.
5) preparing product
Peel off sacrifice layer 4 with acetone as solvent at last, discharge final miniature lithium battery structure (referring to Fig. 6).The product of preparation is as shown in Figure 7.
Embodiment 2
Similar with embodiment 1, its difference is:
In the step 1), substrate 1 is selected quartz substrate for use.Direct current sputtering plated metal Au layer (thickness is 300nm) is as cathode current collector 2a and the anode collector 2b of lower floor (referring to Fig. 2).
Step 2) in, sputtering power is 120W, and the temperature of substrate is 100 ℃ during deposition, and heating rate rises to 400 ℃ from room temperature, and the annealing in process time is 0.5~2h.
The anode of miniature lithium battery of the present invention is original position generation on anode collector Ni layer in the initial charge process.

Claims (4)

1. the preparation method of miniature lithium battery; It is characterized in that said miniature lithium battery is made up of substrate, cathode current collector, cathodic coating, solid electrolyte film, anode film, lower floor's anode collector and upper strata anode collector, substrate is monocrystalline silicon, quartz, pottery or polymer flexibility substrate, and cathode current collector and lower floor's anode collector are prepared on the substrate; Cathodic coating is deposited on the cathode current collector; Solid electrolyte film covers on the cathodic coating, is separated by solid electrolyte film between cathodic coating and the anode film, and said solid electrolyte adopts LiPON; Anode film is positioned on the solid electrolyte film, and the upper strata anode collector is positioned on the anode film; Said cathodic coating is the transition metal oxide cathodic coating; Said anode film is the tin-oxide anode film;
The preparation method of said miniature lithium battery may further comprise the steps:
1) on substrate, deposit layer of metal film as cathode current collector and lower floor's anode collector through chemical deposition or physical deposition method, the material of said metal film is Pt, Au, Ni or Al;
2) on cathode current collector, limit cathode pattern with photoresist; Adopt physical deposition method deposition cathode film then; The method of peeling off with atent solvent is again removed remaining photoresist; Obtain limiting the cathode thin film of figure, annealing in process again, said photoresist is that product type is the photoresist of AZ4620;
3) limit the structure of required solid electrolyte film and anode film with photoresist; Make the structure that limits solid electrolyte film and anode film with photoresist as sacrifice layer (4), said photoresist is that product type is the photoresist of AZ4620;
4) preparation solid electrolyte film, anode film and upper strata anode collector; Said preparation solid electrolyte film, anode film and upper strata anode collector adopt following method: according to the preparation method of cathode thin film; Etch earlier the electrolyte thin film pattern with photoresist; Under the condition of not opening vacuum chamber, method successive sedimentation LiPON film and anode film with magnetron sputtering deposit layer of metal Pt, Au, Ni, Al or Cu more then; Said photoresist is that product type is the photoresist of AZ4620;
5) adopt wet method or dry method to peel off sacrifice layer at last, obtain the miniature lithium battery of complete structure.
2. the preparation method of miniature lithium battery as claimed in claim 1 is characterized in that in step 2) in, the area of said cathode pattern is 0.1~1mm 2, the thickness of said cathode thin film is 0.1~1 μ m.
3. the preparation method of miniature lithium battery as claimed in claim 1 is characterized in that in step 2) in, said cathode thin film is LiCoO 2Film, LiMn 2O 4Film or V 2O 5Film, the area of said cathode thin film are 0.1~1mm 2
4. the preparation method of miniature lithium battery as claimed in claim 1 is characterized in that in step 2) in, said annealing in process is with cathode thin film 300~700 ℃ of annealing in process of warp in oxygen or air; Said physical deposition method adopts magnetron sputtering or pulsed laser deposition.
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