CN1945881A - Full solid thin film lithium battery and its producing method - Google Patents

Full solid thin film lithium battery and its producing method Download PDF

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Publication number
CN1945881A
CN1945881A CNA2006101178990A CN200610117899A CN1945881A CN 1945881 A CN1945881 A CN 1945881A CN A2006101178990 A CNA2006101178990 A CN A2006101178990A CN 200610117899 A CN200610117899 A CN 200610117899A CN 1945881 A CN1945881 A CN 1945881A
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film
solid
thin
metal
micron
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余爱水
王卫江
吴浩青
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Fudan University
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Fudan University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

This invention relates to a full solid film Li cell and its manufacturing method, in which, said cell is composed of one positive film selecting from LiCoO2, V2O5 or LiMn2O4, a solid LiPON electrolyte film between the positive and the negative films, a collector film and a package material film as the sealing. The interface of the electrolyte of full solid film Li cells and the electrode is stable, not crystallized and the mechanical performance is strong and having the storing and working temperature from -55 to 300deg.C capable of enduring high temperature and high pressure while keeping high capacity and circulation performance. Besides, the cell can be processes to a flexible film cell with the thickness of 5-8mum, 8-15mum or over.

Description

All solid-state thin-film lithium battery and manufacture method thereof
Technical field
The present invention relates to a kind of lithium battery, specifically, the present invention relates to a kind of film lithium cell, more particularly, the present invention relates to a kind of all solid-state thin-film lithium battery.Described all solid-state thin-film lithium battery is a kind of brand-new energy storage system, except that have high-energy-density, live forever storage life-span and cycle life, stably the excellent electrochemical properties such as operating voltage, can also be assembled in metal, pottery, silicon chip, macromolecule membrane is in the substrates such as semiconductor chip, only several microns to tens of microns of its thickness, can greatly dwindle does not even need the battery placement space.
Background technology
Fast development along with electronics and information industry, novel portable electronic product and the constantly a large amount of appearances of electric tool as mobile phone, notebook computer and so on,, environmental friendliness little, in light weight to volume, energy form safe and reliable, that energy resource density is high, power is high have proposed new requirement, and lithium rechargeable battery grows up under such situation just.
Devices such as wisdom (energy) card, RF tracking system, radio-frequency (RF) identification sign (RFID tags), some medical apparatus, semiconductor have proposed new higher requirement to the further development of lithium battery.
The smart card of a new generation has very application prospects, and it promptly can be used as credit card, cash card, case record, E-ticket again as atm card.In addition, described smart card also can be used as stock exchange card, electron key, library card, farecard, parking ticket,, purchase card etc.For this reason, the smart card of a new generation requires to have many brand-new functions, for example, supports random asccess memory and keeps the CPU operation, and carry out the finance data transmission of proof of identity and encryption, complicated cryptographic calculation is for the parts on the smart card provide energy or the like.Thereby the smart card of a new generation not only requires to have complexity, multifunctionality, and common built-in miniature chip is with the memory space and the fail safe thereof of guarantee information; Simultaneously, because the physical size of smart card itself and the restriction of flexibility, conventional batteries can not be used for built-in power, and makes flexible thin-film battery become only selection.
In addition, radio-frequency (RF) identification sign (RFID tags) is a kind of information system, and it can be identified device and read information, can be used for differentiating the authenticity of material, for example, and control goods memory space, control figure and physical space.RFID contains a kind of special identifier usually, and for example digital combination is used for identifying information such as the ambient temperature of being collected by transducer, concussion, judges the freshness and the damaged condition of material thus.RFID data storing and conversion have several modes: read-only, and only write and read and write-smear wiping.The radio-frequency (RF) identification sign has very big purposes at the aspects such as management in control logistics, airport security management, station, harbour, parking lot.The tentative check that RFID is used for Eurobank of European Central Bank.At this moment, the fexible film lithium secondary battery becomes only selection once more.
In addition, the safe and reliable minicell of the development need of micro medical electronic therapeutic device guarantees its fail safe.Heart heartstart for example, auditory stimulator and nerve stimulator or the like.
Other purposes of all solid-state thin-film lithium battery also comprises: clock and watch, and portable electric appts, microsensor, lab-on-a-chip, rocket launching and navigation system, petroleum and natural gas is verified and is drilled, or the like.
The full solid thin film lithium secondary battery mainly contains following two big classes by the electrolyte classification:
One class is the lithium ion battery of forming with the organic polymer electrolyte, is also referred to as polymer (or plastics) lithium secondary battery;
Another kind of is the lithium ion battery of forming with inorganic solid electrolyte, is called the inorganic electrolyte lithium secondary battery again.
As the lithium ion battery of the first kind with organic polymer electrolyte composition, for example, there is U.S. Solicore Inc. company to adopt V2O5 as positive pole, Li is as negative pole, utilize the polyimides electrolyte of oneself developing to stack as membrane layer with patent, encapsulate with poly-lithium battery (PLB) plastic-aluminum packaging film commonly used, make the Flexion that thickness is about 0.35mm TMLithium battery.
And for example, Canadian Hygro Quebec company cooperates with the Minnesota Mining and Manufacturing Company, has adopted crosslinked polyethylene glycol oxide (PEO) copolymer in lithium battery, can suppress the formation of Li dendrite preferably, makes the fail safe of battery that essential raising arranged.
Yet, adopt the film lithium cell of polymer technology, its thickness is big slightly, capacity is at several during to dozens of mA, cycle life is at about 500-1000 time, and is more approaching with the polymer Li-ion battery of routine, and the more above-mentioned second class all solid-state thin-film lithium battery of high-rate charge-discharge capability is poor, and, be generally used on the low slightly smart card of degree of integration owing to its bigger area and thickness.
Therefore, though adopt the full solid state polymer lithium ion battery of polymer technology can be prepared into different shape, cycle-index is long, preparation cost is low relatively, but still has a lot of fatal shortcomings: as the interface instability of electrolyte and electrode, easily crystallization, bad mechanical property, to responsive to temperature and Applicable temperature narrow range.
In addition, at semiconductor applications, now, though the FLASH memory has been used on many electronic installations, it also has its limitation.Data can not lost when it needed extra installation battery to guarantee sudden power.NvSRAM (non-volatile Static Random Access Memory) has accounted for 80% share in communication and network.Though now, disposable button cell can be used on the nvSRAM, it must manually load up, and this just needs more artificial and headspace.The nvSRAM manufacturing process must be through 260 degree welding and water-washing process subsequently, and the above-mentioned second class full solid thin film battery meets this requirement.
As the second class solid-State Thin Film Li-Ion Batteries of forming with inorganic solid electrolyte, the inorganic solid electrolyte material has the mechanical strength height, do not contain inflammable and volatile component, do not exist in the dead of night, the resisting temperature performance is good, simultaneously, solid inorganic material can be prepared into film, is easy to the lithium battery subminaturization.And, by storage life and the cycle performance that the film inorganic solid electrolyte lithium secondary battery of inorganic material assembling has overlength, be fit to do the Power Support of each electronic product.
Chargeable full-solid film lithium cell and lithium ion battery have U.S.'s Oak Ridge National Laboratory to begin development the earliest.After this, the someone adopts TiS 2Or MoS 2As target, under the atmosphere that aerobic exists, deposit TiO 0.2S 1.4Or MoO 1.6S 1.8Film deposits the glassy state oxide electrolyte then as positive pole, and last vacuum evaporation lithium anode, outermost adopt the hydrophobic polymer packing.Whole hull cell core thickness is less than 10 μ m, and final products (comprising encapsulating film) thickness is less than 0.1mm.The battery table area is 2cm 2, average output voltage 2.0V, maximum current density is 200 μ Acm 2, battery capacity is controlled at 5-300 μ Ahcm -2, cycle life is above 10000 times.
And for example, EBC (Eveready Battery Company) company has developed all solid state Li-TiS 2Storage battery.Its method is: at first, and sputtered with Ti S 2Positive pole is being separated, and adopts target 6Li-4Li 3PO 4-P 2S 5Sputter oxygen sulfuration glassy state electrolyte, last vacuum evaporation lithium anode.But, use to find that lithium anode and electrolyte can react and form the Li of one deck high impedance 2The S layer, thus charge-discharge performance influenced.For this reason, adopted vacuum evaporation Li between lithium anode and electrolyte, to prevent the two direct contact.The total conductivity of whole electrolyte and LiI layer is 2 * 10 -6Scm -1, whole hull cell thickness is about 10 μ m, area 10cm 2, charging/discharging voltage 1.4-2.8V, maximum current density is 300 μ Acm 2, battery capacity is controlled at 5-100 μ Ahcm -2, cycle life is above 1000 times.But above-mentioned two kinds of film lithium cells are Li-TiS 2Storage battery, its cycle life is respectively only 10000 times and 1000 levels.Voltage is also with LiCoO 2, LiMn 2O 4For the battery of positive pole low.
American I nfinite Power Solutions-ITN Energy Systems company has developed a kind of LiTE*STAR TMThe series all solid-state thin-film lithium battery, the positive pole of this all solid-state thin-film lithium battery adopts LiCoO 2, negative pole is a lithium metal, electrolyte is LiPON, 12 microns of thickness.Its fundamental characteristics is: discharging current reaches 20mAcm 2, impedance is about 150 Ω cm 2, storage temperature is at-50-180 degree, and working temperature is at-50-120 degree, and cycle life can reach 60000 times.
The POWER Fab of U.S. Cymbat company development TMThe series all solid-state thin-film lithium battery, its thickness 5-25 micron.The anodal LiCoO that adopts 2, negative pole is a lithium metal, electrolyte is LiPON, 12 microns of thickness.Has 300Whkg -1High-energy-density, volume and capacity ratio is 1000WhL -1, sustainable work under the low temperature of-25 degree, cycle life can reach 70000 times.High-multiplying power discharge, 50C can reach 80% of design capacity during discharge.
But the anti-air of all solid-state thin-film lithium battery of above-mentioned two u s companys, the ability of water vapor permeable not reach further raising, it stores, temperature range of work is limited.
It is the United States Patent (USP) of " film lithium cell " (Thin Lithium Film Battery.) for " U.S.6,242,129 ", denomination of invention that the United States Patent (USP) technology of similarly relevant all solid-state thin-film lithium battery also can be enumerated U.S. Patent number.
Number of patent application discloses a kind of chargeable film lithium cell for the Chinese patent application technology of " 03804888.4 ", and described battery comprises that part is by the battery unit of housing (36) encapsulation at least.This battery unit is included in negative electrode (18) and cathode current collector (16) and the permeable anode current collector (24) on the substrate (12), negative electrode (18) and cathode current collector (16) are electrically coupled to one another and are electrically coupled to electrolyte (20), and permeable anode current collector (24) has and is electrically coupled to electrolytical first surface and opposing second surface.Permeable anode current collector (24) thickness is less than about 0.1 micron.Coating on the opposing second surface of common anode current collector has been omitted.Positive terminal and negative terminal (34,32) are electrically connected to this battery unit.But this rechargeable thin film battery exists and the bigger difference of the present invention, and its manufacture method is different with the present invention, and cost of manufacture is obviously higher, the manufacturing process instability.
Number of patent application is that the Chinese patent of " 200510028248.X " discloses " equipment of a kind of " original position " deposition all solid-state thin-film lithium battery, and adopt this equipment to prepare the method for all solid-state thin-film lithium battery.This equipment is composed in series by four deposit film chambers and a glove box, and different films prepare in four different chambers respectively: the magnetically controlled DC sputtering chamber prepares that electronics collector film, direct current or rf magnetron sputtering chamber prepare cathode thin film, the rf magnetron sputtering chamber prepares electrolytic thin-membrane and the vacuum thermal evaporation chamber prepares the lithium metal anode film.The present invention has realized " original position " deposition of various films under the condition of not destroying vacuum, avoided between film the interface to be stain by dust, moisture and other pollutants.Adopt all solid-state thin-film lithium battery of this equipment preparation to have less interface resistance and charge transfer resistance, in charge and discharge cycles, show less capacity fade performance.But this application patent does not have any announcement to all solid-state thin-film lithium battery, the protection and the subsequent packet thereof of lithium metal is not equipped with any statement yet.
Number of patent application discloses a kind of all solid-state thin-film lithium battery and preparation method thereof for the Chinese patent of " 200410067342.1 ".This film lithium cell is made of lithium phosphate (LiPON) electrolytic thin-membrane and argent film three parts of metal collector, nitrogenize.Its advantage is in the preparation process of battery; do not need the very active lithium metal of sedimentation chemistry character as anode, the anode of lithium metal as battery but electrochemical reaction in-situ deposition between electrolytic thin-membrane and metal collector takes place when utilizing the charging of argent and lithium phosphate.But this patent is not further specified to performance, physical state, the cycle life of its film lithium cell yet.The electric weight of this hull cell relies on positive electrode fully, only suitable lithium metal oxide and be not suitable for not containing the oxide such as the V of lithium 2O 5
Number of patent application discloses a kind of hull cell and preparation method thereof for the Chinese patent of " 200410084572.9 ".It is configured to the film energy-storage system based on metallic aluminium and iodine.This hull cell can provide low current density in μ A/cm2 order of magnitude scope, and discharge platform is at 400mV～1000mV.Discharge capacity is at 100～102 μ Ah/cm2.The I2/Al hull cell can prepare on a large scale, and method is simple.Because the lightweight of Al is nontoxic, advantages such as cheapness, the I2/Al hull cell is compared with other battery, has low cost, characteristics such as safe in utilization and environmental friendliness.Be particularly suitable for as pacemaker, smart card, the device of portable medical science, the power supply in the micro mechanical system (MEMS).But this hull cell is anode with aluminium, and iodine is negative electrode, and the hyrate of silver iodide or solution are electrolyte.Obviously, with the desired all solid-state thin-film lithium battery of latest development sizable difference is arranged.In addition, this patent is equally not further specified to performance, physical state, the cycle life of its film lithium cell yet.
In addition, as smart card or radio-frequency (RF) identification sign card etc., in manufacturing process, all need through high temperature (130 ℃ to 150 ℃), high pressure (~ 200N/cm 2) extrusion modling and can keep the capacity and the cycle performance of battery.In some other occasion, also need the ability of the anti-air of further raising, water vapor permeable badly.
Summary of the invention
In view of above-mentioned, the objective of the invention is to: a kind of all solid-state thin-film lithium battery is provided, the electrolyte of described all solid-state thin-film lithium battery and the interface stability of electrode, be difficult for crystallization, mechanical performance is strong.Have from the storage and the working temperature of-55 degree-300 degree scopes.Can stand high temperature, in the time of the extrusion modling of high pressure, keep the high power capacity and the cycle performance of battery.In addition, all solid-state thin-film lithium battery of the present invention can make thickness respectively at 5-8 micron, 8-15 micron and the flexible thin-film battery more than 15 microns, and the ability of anti-air, water vapor permeable is stronger.Cycle life can reach 40000-50000 time.
Purpose of the present invention is again: a kind of manufacture method of all solid-state thin-film lithium battery is provided, the electrolyte of described all solid-state thin-film lithium battery and the interface stability of electrode, be difficult for crystallization, mechanical performance is strong.Have from the storage and the working temperature of-55 degree-300 degree scopes.Can stand high temperature, in the time of the extrusion modling of high pressure, keep the high power capacity and the cycle performance of battery.In addition, all solid-state thin-film lithium battery of the present invention can make thickness respectively at 5-8 micron, 8-15 micron and the flexible thin-film battery more than 15 microns, and the ability of anti-air, water vapor permeable is stronger, and cycle life can reach 40000-50000 time.According to the manufacture method of all solid-state thin-film lithium battery of the present invention, cost is lower, and the scale of being convenient to is commercially produced.
According to all solid-state thin-film lithium battery of the present invention, described all solid-state thin-film lithium battery is packed by anode thin film, the solid electrolyte film between anode thin film, negative film, the collector body film that is connected with positive and negative electrode respectively and packaging material film and constitutes, and described positive electrode is for being selected from LiCoO 2, V 2O 5, LiMn 2O 4A kind of metal oxide, described negative material is selected from material with carbon element, SnN xWith any of lithium metal, described solid electrolyte is LiPON, and the described collector body film that is connected with positive and negative electrode is a thin metal layer, and described packaging material are the composite multilayer membrane of metal/high-molecular material.
Be preferably, according to all solid-state thin-film lithium battery of the present invention, described all solid-state thin-film lithium battery is formed on any base material that is selected from pottery, chip, macromolecular material, glass, metal etc.
Be preferably,, be selected from a kind of of gold, nickel as the thin metal layer of described positive and negative electrode collector body according to all solid-state thin-film lithium battery of the present invention.
Being preferably, according to all solid-state thin-film lithium battery of the present invention, is aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound as the composite multilayer membrane of the metal/high-molecular material of described packaging material.
Be preferably, according to all solid-state thin-film lithium battery of the present invention, the lithium metal thin layer of described negative material has a Parylene (Parylene) protective layer outward.
Be preferably,, do not comprise the film lithium cell gross thickness 5-8 micron of substrate according to all solid-state thin-film lithium battery of the present invention.
Be preferably, according to all solid-state thin-film lithium battery of the present invention, the film lithium cell gross thickness that does not comprise substrate is the 8-15 micron.
Be preferably, according to all solid-state thin-film lithium battery of the present invention, the film lithium cell gross thickness that does not comprise substrate is at the 15-50 micron.
Be preferably, according to all solid-state thin-film lithium battery of the present invention, the thin layer thickness of described negative pole is at the 2-8 micron.
Be preferably, according to all solid-state thin-film lithium battery of the present invention, the metal oxide thickness of described positive pole is at the 2-8 micron.
Be preferably, according to all solid-state thin-film lithium battery of the present invention, described dielectric substrate thickness is at the 1-2 micron.
Be preferably, according to all solid-state thin-film lithium battery of the present invention, described collector body thickness is at the 0.1-0.5 micron.
According to the present invention, the full solid thin film battery is constructed in a substrate, and the inorganic energy storage film of multilayer prepares in substrate by physics or chemical method.LiPON isolates positive pole and negative pole as electrolyte, and positive pole is generally lithium and cobalt oxides or lithium manganese oxide or vanadium oxide (LiCoO 2, V 2O 5, LiMn 2O 4), negative pole is generally Sn 3N 4Or lithium metal, last cell package.Since do not exist any other the reaction, electric energy and chemical energy be converted into 100%.
According to the present invention, LiPON isolates positive pole and negative pole as electrolyte, the anodal lithium and cobalt oxides (LiCoO that adopts 2), can obtain high-discharge-rate, high discharge voltage up to 100C.
According to the present invention, LiPON isolates positive pole and negative pole as electrolyte, and negative pole adopts lithium metal, and then maximum operating temperature can reach 170 degree, adopts Sn 3N 4The time, then maximum operating temperature can reach 300 degree.
According to the present invention, LiPON isolates positive pole and negative pole as electrolyte, and negative pole adopts lithium metal or Sn 3N 4, described packaging material adopt the composite multilayer membrane of metal/high-molecular material, for aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound, then can improve the anti-air of hull cell of the present invention, the ability of water vapor permeable greatly.
According to the present invention, LiPON isolates positive pole and negative pole as electrolyte, and negative pole adopts lithium metal or Sn 3N 4, the lithium metal thin layer of described negative material is outside equipped with a Parylene (Parylene) protective layer, thus, can strengthen the electrochemical reaction performance and the efficient of lithium metal.The battery minimum operating temperature can reach-55 degree.
According to the present invention, LiPON gets the 1-2 micron as the thickness of electrolyte isolated film, is the 2-8 micron as the lithium metal or the Sn3N4 thickness of thin layer of negative pole, as lithium and cobalt oxides or the lithium manganese oxide or the vanadium oxide (LiCoO of positive pole 2, V 2O 5, LiMn 2O 4) the thickness of film get the 2-8 micron, get the 2-50 micron as the thickness of the composite multilayer membrane film of the metal/high-molecular material of described packing film, described collector body thickness is at the 0.1-0.5 micron.Thus, each thin layer thickness of all solid-state thin-film lithium battery of the present invention capable of being combined, form its battery (not comprising basalis) thickness and be respectively less than 5-8 micron, 8-15 micron and the flexible all solid-state thin-film lithium battery more than 15 microns, described all solid-state thin-film lithium battery with different-thickness has flexible good respectively or feature such as capacity is big.
The chemical property that table 1 has compared battery best on chargeable full-solid film lithium cell of the present invention and lithium ion battery and the present market compares.The energy density of full solid thin film battery can be 4 times of lithium ion battery up to 1000WH/G.Cycle life more is 4-5 ten thousand times.
Table 1 battery performance relatively
The Ni-Cr battery type Specific energy (Wh/kg) Volumetric specific energy (Wh/l) Specific energy (W/kg) Cycle life
Ni-Cr battery 80 150 500 400
The ni-mh electrochemical cell 150 250 200 600
The liquid state lithium ion battery 140 400 300 500
Poly-lithium battery 180 300 480 500
Film lithium ion battery 250 1,041 2,500 1,000
Film lithium cell of the present invention 300 959 6,000 40,000
Manufacture method according to all solid-state thin-film lithium battery of the present invention, described all solid-state thin-film lithium battery is packed by anode thin film, the solid electrolyte film between anode thin film, negative film, the collector body film that is connected with positive and negative electrode respectively and packaging material film and constitutes, and described positive electrode is for being selected from LiCoO 2, V 2O 5, LiMn 2O 4A kind of metal oxide, described negative material is selected from material with carbon element, SnN xWith any of lithium metal, described solid electrolyte is LiPON, and the described collector body film that is connected with positive and negative electrode is a thin metal layer, and described packaging material are the composite multilayer membrane of metal/high-molecular material.
The manufacture method of all solid-state thin-film lithium battery of the present invention comprises following operation:
1. the cleaning of substrate
HCl with 1M cleans to substrate, cleans 3-5 time oven dry then with distilled water;
2. the making of positive electrode collector
Dc sputtering is made positive electrode collector, and gold target makes the about 0.1-0.5 micron of positive electrode collector thickness;
3. Zheng Ji making
10 -3-10 -5Under the vacuum degree of Pa, in oxygen atmosphere, with the corresponding metal oxide film is target, the rf magnetron sputtering deposition is anodal, magnetron sputtering power is 100-500W, magnetron sputtering speed be the 0.2-2 micron/hour, flowing velocity is 10-50sccm, the metal-oxide film thickness of sputtering sedimentation is at the 2-5 micron;
4. the making of solid electrolyte
In blanket of nitrogen, LiPON inorganic electrolyte liquid is by radio frequency sputtering Li 3PO 4Target is deposited on the anode thin film, thickness 1-2 micron;
5. the making of negative pole
10 -3-10 -5Under the vacuum degree of Pa, in argon gas atmosphere, vacuum vapour deposition heating lithium source or material with carbon element or SnN x, plated metal lithium or material with carbon element or SnN on the LiPON dielectric substrate xThin layer is as negative pole;
6. the interpolation of both positive and negative polarity collector body
By welding or metal-sol metal levels such as metallic nickel are connected with both positive and negative polarity;
7. the composite multilayer membrane of package metals/macromolecular material is aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound.
Nationality is by above-mentioned operation 3,10 -3-10 -5Under the vacuum degree of Pa, in oxygen atmosphere, with the corresponding metal oxide film is target, rf magnetron sputtering deposition is anodal, and magnetron sputtering power is 100-500W, magnetron sputtering speed be the 0.2-2 micron/hour, flowing velocity is 10-50sccm, can obtain the cathode film that thickness is the 2-5 micron, by analysis, film is smooth evenly.
Nationality is by above-mentioned operation 3,10 -3-10 -5Under the vacuum degree of Pa, in argon gas atmosphere, vacuum vapour deposition heating lithium source or material with carbon element or SnN x, plated metal lithium or material with carbon element or SnN on the LiPON dielectric substrate xThin layer can obtain the negative electrode film less than 5 microns as negative pole.
Nationality is by above-mentioned operation 7, and the composite multilayer membrane of package metals/macromolecular material is aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound, can obtain to prevent that sealing, air enter the effect of battery and lithium metal reaction, prolongs the use and the storage life of battery.
Be preferably, according to the manufacture method of all solid-state thin-film lithium battery of the present invention, the base material of described all solid-state thin-film lithium battery is for being selected from any of pottery, chip, macromolecular material, glass, metal etc.
Be preferably,, be selected from a kind of of gold, nickel, platinum, copper, cobalt as the thin metal layer of described positive and negative electrode collector body according to the manufacture method of all solid-state thin-film lithium battery of the present invention.
Being preferably, according to the manufacture method of all solid-state thin-film lithium battery of the present invention, is aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound as the composite multilayer membrane of the metal/high-molecular material of described packaging material.
Be preferably,, after operation 5, the protection operation of a lithium metal arranged according to the manufacture method of all solid-state thin-film lithium battery of the present invention:
Evaporation is coated with a Parylene (Parylene) protective layer outside the lithium metal thin layer of described negative material.
Nationality is coated with a Parylene (Parylene) protective layer by evaporation outside the lithium metal thin layer of described negative material, can make lithium not react with wrapper, because Parylene falls between, makes lithium metal not contact with wrapper.
Be preferably, according to the manufacture method of all solid-state thin-film lithium battery of the present invention, the film lithium cell gross thickness that does not comprise substrate is less than 8 microns.Better is that the above-mentioned film lithium cell gross thickness of substrate that do not comprise is at the 5-8 micron.
Be preferably, according to the manufacture method of all solid-state thin-film lithium battery of the present invention, the film lithium cell gross thickness that does not comprise substrate is the 8-15 micron.Better is that the above-mentioned film lithium cell gross thickness of substrate that do not comprise is at the 8-10 micron.
Be preferably, according to the manufacture method of all solid-state thin-film lithium battery of the present invention, the film lithium cell gross thickness that does not comprise substrate is at the 15-50 micron.Better is that the above-mentioned film lithium cell gross thickness of substrate that do not comprise is at the 20-40 micron.Thus, can increase other performances such as capacity that reach all solid-state thin-film lithium battery ...
Be preferably, according to the manufacture method of all solid-state thin-film lithium battery of the present invention, the thin layer thickness of described negative pole is at the 2-8 micron.Better is that described thickness is at the 1-2 micron.
Be preferably, according to the manufacture method of all solid-state thin-film lithium battery of the present invention, the metal oxide thickness of described positive pole is at the 2-8 micron.Better is that described thickness is at the 1-2 micron.
Be preferably, according to the manufacture method of all solid-state thin-film lithium battery of the present invention, described dielectric substrate thickness is at the 1-2 micron.Better is that described thickness is at the 1-2 micron.
Be preferably, according to the manufacture method of all solid-state thin-film lithium battery of the present invention, described Parylene (Parylene) protective layer thickness is at the 1-30 micron.Better is that described thickness is at the 1-2 micron.
Description of drawings
Figure 1 shows that the structural representation of all solid-state thin-film lithium battery of the present invention.
Figure 2 shows that the cycle performance figure of all solid-state thin-film lithium battery one example of the present invention.
Figure 3 shows that the cycle performance figure of all solid-state thin-film lithium battery one example of the present invention.
Figure 4 shows that the outside drawing that is deposited on suprabasil all solid-state thin-film lithium battery one example of thin polymer film of the present invention.
Figure 5 shows that all solid-state thin-film lithium battery one example of the present invention charging and discharging curve figure when 25 spend.
Figure 6 shows that all solid-state thin-film lithium battery one example of the present invention charging and discharging curve figure when 150 spend.
Figure 7 shows that all solid-state thin-film lithium battery one example of the present invention discharges and recharges the graph of a relation with period when 150 spend.
Figure 8 shows that the outside drawing of all solid-state thin-film lithium battery one example of the present invention.
Concrete execution mode
Below, with reference to accompanying drawing, specify the present invention for embodiment.
Embodiment 1
See Fig. 1.Described all solid-state thin-film lithium battery is packed by anode thin film, the solid electrolyte film between anode thin film, negative film, the collector body film that is connected with positive and negative electrode respectively and packaging material film and constitutes, and described positive electrode is LiCoO 2, described negative material is SnN x, described solid electrolyte is LiPON, the described collector body film that is connected with positive and negative electrode is an au film coating, is aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound as the composite multilayer membrane of the metal/high-molecular material of described packaging material.
At first, carry out the cleaning of substrate.HCl with 1M cleans to macromolecular material substrate (12-75 micron), cleans 3 times oven dry then with distilled water.Then, direct current sputtering is made positive electrode collector, and gold target makes the about 0.1-0.2 micron of positive electrode collector thickness.
Then, 10 -3-10 -5Under the vacuum degree of Pa, in oxygen atmosphere, with LiCoO 2Be target, rf magnetron sputtering deposition is anodal, and magnetron sputtering power is 100-200W, magnetron sputtering speed be the 0.2-1 micron/hour, flowing velocity is 10-20sccm, the metal-oxide film thickness of sputtering sedimentation is at the 2-5 micron.
Then, in blanket of nitrogen, LiPON inorganic electrolyte liquid is by radio frequency sputtering Li 3PO 4Target is deposited on the anode thin film, thickness 1-2 micron.
10 -3-10 -5Under the vacuum degree of Pa, in argon gas atmosphere, vacuum vapour deposition heating SnN xThe source deposits SnN on the LiPON dielectric substrate xThin layer is as negative pole.In addition, the interpolation of both positive and negative polarity collector body is connected metal levels such as metallic nickel and carries out by welding or metal-sol with both positive and negative polarity.As the composite multilayer membrane of package metals/macromolecular material, with aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound by hot sealing.Thus, make all solid-state thin-film lithium battery of the present invention.Described all solid-state thin-film lithium battery as shown in Figure 4.Its battery gross thickness that does not comprise substrate is at 6 microns.
As shown in Figure 3, all solid-state thin-film lithium battery of present embodiment, if anodal thickness is 2 microns, the battery circulation surpasses 2,000 times, also keeps the capacity about 85%.
Embodiment 2
Except following difference, other are as figure embodiment 1.
Described negative material is a lithium metal, and pottery is adopted in substrate.
HCl with 1M cleans to the ceramic material substrate, cleans 5 times oven dry then with distilled water.Then, direct current sputtering is made positive electrode collector, and gold target makes the about 0.3-0.5 micron of positive electrode collector thickness.
Then, 10 -3-10 -5Under the vacuum degree of Pa, in oxygen atmosphere, with LiCoO 2Be target, rf magnetron sputtering deposition is anodal, and magnetron sputtering power is 200-300W, magnetron sputtering speed be the 0.8-2 micron/hour, flowing velocity is 20-30sccm, the metal-oxide film thickness of sputtering sedimentation is at the 2-5 micron.
Then, in blanket of nitrogen, LiPON inorganic electrolyte liquid is by radio frequency sputtering Li 3PO 4Target is deposited on the anode thin film, thickness 1-2 micron.
10 -3-10 -5Under the vacuum degree of Pa, in argon gas atmosphere, vacuum vapour deposition heating of metal lithium source, plated metal lithium thin layer is as negative pole on the LiPON dielectric substrate.Thickness 2-3 micron.
As the composite multilayer membrane of package metals/macromolecular material, with aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound by hot sealing. 5 microns of thickness.
Thus, make all solid-state thin-film lithium battery of the present invention.Described all solid-state thin-film lithium battery as shown in Figure 8.Its battery gross thickness that does not comprise substrate is at 15 microns.
Embodiment 3
Except following difference, other are as figure embodiment 1.
Positive electrode is LiMn 2O 4, described negative material is a lithium metal, pottery is adopted in substrate.
HCl with 1M cleans to the ceramic material substrate, cleans 5 times oven dry then with distilled water.Then, direct current sputtering is made positive electrode collector, and gold target makes the about 0.3-0.5 micron of positive electrode collector thickness.
Then, 10 -3-10 -5Under the vacuum degree of Pa, in oxygen atmosphere, with LiMn 2O 4Be target, rf magnetron sputtering deposition is anodal, and magnetron sputtering power is 300-400W, magnetron sputtering speed be the 0.8-2 micron/hour, flowing velocity is 30-40sccm, the LiMn of sputtering sedimentation 2O 4Film thickness is at the 2-5 micron.
Then, in blanket of nitrogen, LiPON inorganic electrolyte liquid is by radio frequency sputtering Li 3PO 4Target is deposited on the anode thin film, thickness 1-2 micron.
10 -3-10 -5Under the vacuum degree of Pa, in argon gas atmosphere, vacuum vapour deposition heating of metal lithium source, plated metal lithium thin layer is as negative pole on the LiPON dielectric substrate.Thickness 2-3 micron.
Evaporation is coated with a Parylene (Parylene) protective layer outside the lithium metal thin layer of described negative material.
As the composite multilayer membrane of package metals/macromolecular material, with aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound by hot sealing. 5 microns of thickness.
Thus, make all solid-state thin-film lithium battery of the present invention.Described all solid-state thin-film lithium battery as shown in Figure 8.Its battery gross thickness that does not comprise substrate is at 18 microns.
Embodiment 4
Except following difference, other are as figure embodiment 1.
Described negative material is a lithium metal, and metal is adopted in substrate.
HCl with 1M cleans to the metal material substrate, cleans 5 times oven dry then with distilled water.Then, direct current sputtering is made positive electrode collector, and gold target makes the about 3-5 micron of positive electrode collector thickness.
Then, 10 -3-10 -5Under the vacuum degree of Pa, in oxygen atmosphere, with LiCoO 2Be target, rf magnetron sputtering deposition is anodal, and magnetron sputtering power is 300-500W, magnetron sputtering speed be the 1-1.5 micron/hour, flowing velocity is 35-45sccm, the metal-oxide film thickness of sputtering sedimentation is at the 2-5 micron.
Then, in blanket of nitrogen, LiPON inorganic electrolyte liquid is by radio frequency sputtering Li 3PO 4Target is deposited on the anode thin film, 2 microns of thickness.
10 -3-10 -5Under the vacuum degree of Pa, in argon gas atmosphere, vacuum vapour deposition heating of metal lithium source, plated metal lithium thin layer is as negative pole on the LiPON dielectric substrate.Thickness 5-8 micron.
Evaporation is coated with a Parylene (Parylene) protective layer outside the lithium metal thin layer of described negative material.
As the composite multilayer membrane of package metals/macromolecular material, with aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound by hot sealing. 15 microns of thickness.
Thus, make all solid-state thin-film lithium battery of the present invention.Described all solid-state thin-film lithium battery as shown in Figure 8.Its battery gross thickness that does not comprise substrate is at 36 microns.
Embodiment 5
Except following difference, other are as figure embodiment 1.
Described positive electrode is V 2O 5, described negative material is a lithium metal, metal is adopted in substrate.
HCl with 1M cleans to the metal material substrate, cleans 3 times oven dry then with distilled water.Then, direct current sputtering is made positive electrode collector, and the nickel target makes the about 3-5 micron of positive electrode collector thickness.
Then, 10 -3-10 -5Under the vacuum degree of Pa, in oxygen atmosphere, with V 2O 5Be target, rf magnetron sputtering deposition is anodal, and magnetron sputtering power is 300-500W, magnetron sputtering speed be the 1-1.5 micron/hour, flowing velocity is 35-45sccm, the V of sputtering sedimentation 2O 5Film thickness is at the 2-5 micron.
Then, in blanket of nitrogen, LiPON inorganic electrolyte liquid is by radio frequency sputtering Li 3PO 4Target is deposited on the anode thin film, 2 microns of thickness.
10 -3-10 -5Under the vacuum degree of Pa, in argon gas atmosphere, vacuum vapour deposition heating of metal lithium source, plated metal lithium thin layer is as negative pole on the LiPON dielectric substrate.Thickness 5-8 micron.
Evaporation is coated with a Parylene (Parylene) protective layer outside the lithium metal thin layer of described negative material.
As the composite multilayer membrane of package metals/macromolecular material, with aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound by hot sealing. 15 microns of thickness.
Thus, make all solid-state thin-film lithium battery of the present invention.Described all solid-state thin-film lithium battery as shown in Figure 8.Its battery gross thickness that does not comprise substrate is at 26 microns.
Owing to adopt inorganic solid-state electrolytic solution, the temperature that full solid thin film battery ability is more much higher than common batteries.If use lithium metal as negative pole, the highest temperature can reach 170 degree.If the block polymer of use lithium such as nitrogenize tin are as negative pole, the highest temperature can reach 300 degree.So good temperature characterisitic has been arranged, in the preparation process of electronic device, just can unite two into one electronic component and battery.The storage of full solid thin film battery and working temperature have very wide scope, can be from-55 degree 300 degree.
Performance evaluation
The battery cycle-index:
The battery of embodiment 2-5 as shown in Figure 2, if anodal thickness is the 0.05-2 micron, cycle-index can reach 40,000 5 thousand times.Through 40,000 5 thousand circulations, can also keep 95% battery capacity.
The discharge characteristic of battery:
The capacity of full solid thin film battery and discharge characteristic are just depending on battery, and the selection of negative material is if use LiCoO 2As positive pole, can obtain high-discharge-rate, high discharge voltage.If use V 2O 5As positive pole, though the discharge of battery low range, capacity can be doubled and redoubled.
The plasticity of battery
The full solid thin film battery can be deposited on the macromolecule plastic film (12-75 micron), as shown in Figure 4., can reduce production costs greatly as substrate with macromolecule plastic film, and increase the plasticity of battery, flexibility.Battery can be made arbitrary shape, and can bending fold.
High-rate discharge ability
Most of batteries are subjected to its internal resistance and in the thermal impact of crossing of high-multiplying power discharge, fill, and discharge-rate is all less than 2C.But the discharge-rate of full solid thin film battery of the present invention can reach 100C.
The high temperature discharge performance:
Chargeable battery is when 60 degree use in the market, and capacity can fail significantly.Sometimes also with gas release action, leakage, even the danger of blast is arranged.But the operating temperature range of full solid thin film battery of the present invention is generally-40 spends to 150 degree.Sometimes more can wide extremely-55-degree to 300 degree.This feature makes this battery can be used for some maximum conditions, as the pyrostat in the semiconductor fabrication, and drilling engineering and aerospace engineering.
Fig. 5 and Fig. 6 are respectively the charge-discharge performance of full solid thin film battery of the present invention when 25 degree and 150 are spent.Fig. 7 is the charge-discharge performance of battery of the present invention when 150 spend.As can be seen, the enclosed pasture efficient of battery is 100%, and at the 200th circulation time, capacity has only lost 20%.
According to above-mentioned, the invention provides the manufacture method that a kind of all solid-state thin-film lithium battery is provided, the electrolyte of described all solid-state thin-film lithium battery and the interface stability of electrode, be difficult for crystallization, mechanical performance is strong.Have from the storage and the working temperature of-55 degree-300 degree scopes.Can stand high temperature, in the time of the extrusion modling of high pressure, keep the high power capacity and the cycle performance of battery.In addition, all solid-state thin-film lithium battery of the present invention can make thickness respectively at 5-8 micron, 8-15 micron and the flexible thin-film battery more than 15 microns, and the ability of anti-air, water vapor permeable is stronger, and cycle life can reach 40000-50000 time.。According to the manufacture method of all solid-state thin-film lithium battery of the present invention, cost is lower, and the scale of being convenient to is commercially produced.

Claims (9)

1. all solid-state thin-film lithium battery, described all solid-state thin-film lithium battery is packed by anode thin film, negative film, the solid electrolyte film between anode thin film, negative film, the collector body film that is connected with positive and negative electrode respectively and packaging material film and constitutes, it is characterized in that
Described positive electrode is for being selected from LiCoO 2, V 2O 5, LiMn 2O 4A kind of metal oxide, described negative material is selected from material with carbon element, SnN xWith any of lithium metal, described solid electrolyte is LiPON, and the described collector body film that is connected with positive and negative electrode is a thin metal layer, and described packaging material are the composite multilayer membrane of metal/high-molecular material.
2. all solid-state thin-film lithium battery as claimed in claim 1 is characterized in that described all solid-state thin-film lithium battery is formed on any base material that is selected from pottery, chip, macromolecular material, glass, metal etc.
3. all solid-state thin-film lithium battery as claimed in claim 1 is characterized in that, the thin metal layer of described positive and negative electrode collector body is selected from a kind of of gold, nickel, platinum, copper, cobalt.
4. all solid-state thin-film lithium battery as claimed in claim 1 is characterized in that, the composite multilayer membrane of the metal/high-molecular material of described packaging material is aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound.
5. all solid-state thin-film lithium battery as claimed in claim 1 is characterized in that, the lithium metal thin layer of described negative material has a Parylene protective layer outward.
6. all solid-state thin-film lithium battery as claimed in claim 1 is characterized in that, does not describedly comprise that the film lithium cell gross thickness of substrate is the 5-8 micron, or the 8-15 micron, or the 15-50 micron.
7. all solid-state thin-film lithium battery as claimed in claim 1, it is characterized in that the thin layer thickness of described negative pole is at the 2-8 micron, the metal oxide thickness of described positive pole is at the 2-8 micron, described dielectric substrate thickness is at the 1-2 micron, and described collector body thickness is at the 0.1-0.5 micron.
8. the manufacture method of an all solid-state thin-film lithium battery, described all solid-state thin-film lithium battery is packed by anode thin film, the solid electrolyte film between anode thin film, negative film, the collector body film that is connected with positive and negative electrode respectively and packaging material film and constitutes, and described positive electrode is for being selected from LiCoO 2, V 2O 5, LiMn 2O 4A kind of metal oxide, described negative material is selected from material with carbon element, SnN xWith any of lithium metal, described solid electrolyte is LiPON, and the described collector body film that is connected with positive and negative electrode is a thin metal layer, and described packaging material are the composite multilayer membrane of metal/high-molecular material, it is characterized in that, described manufacture method comprises following operation:
(1) cleaning of substrate
HCl with 1M cleans to substrate, cleans 3-5 time oven dry then with distilled water;
(2) making of positive electrode collector
Direct current sputtering is sent out the making positive electrode collector, and gold target makes the about 0.1-0.5 micron of positive electrode collector thickness;
(3) Zheng Ji making
10 -3-10 -5Under the vacuum degree of Pa, in oxygen atmosphere, with the corresponding metal oxide film is target, the rf magnetron sputtering deposition is anodal, magnetron sputtering power is 100-500W, magnetron sputtering speed be the 0.2-2 micron/hour, gas flow rates is 10-50sccm, the metal-oxide film thickness of sputtering sedimentation is at the 2-5 micron;
(4) making of solid electrolyte
In blanket of nitrogen, LiPON inorganic electrolyte liquid is by radio frequency sputtering Li 3PO 4Target is deposited on the anode thin film, thickness 1-2 micron;
(5) making of negative pole
10 -3-10 -5Under the vacuum degree of Pa, in argon gas atmosphere, vacuum vapour deposition heating lithium source or material with carbon element or SnN x, plated metal lithium or material with carbon element or SnN on the LiPON dielectric substrate xThin layer is as negative pole;
(6) interpolation of both positive and negative polarity collector body
By welding or metal-sol metal levels such as metallic nickel are connected with both positive and negative polarity;
(7) composite multilayer membrane of package metals/macromolecular material is aluminium/polyethylene multilayer compound or aluminium/polypropylene multi-layer compound.
9. the manufacture method of all solid-state thin-film lithium battery as claimed in claim 8 is characterized in that, in operation (5) afterwards, the protection operation of a lithium metal is arranged:
Evaporation is coated with a Parylene protective layer outside the lithium metal thin layer of described negative material.
CNA2006101178990A 2006-11-02 2006-11-02 Full solid thin film lithium battery and its producing method Pending CN1945881A (en)

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