CN102832412B - Method for encapsulating all-solid thin film lithium ion battery, encapsulating material thereof and method for preparing encapsulating material - Google Patents
Method for encapsulating all-solid thin film lithium ion battery, encapsulating material thereof and method for preparing encapsulating material Download PDFInfo
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- CN102832412B CN102832412B CN201210338375.XA CN201210338375A CN102832412B CN 102832412 B CN102832412 B CN 102832412B CN 201210338375 A CN201210338375 A CN 201210338375A CN 102832412 B CN102832412 B CN 102832412B
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Abstract
The invention relates to a method for encapsulating an all-solid thin film lithium ion battery, an encapsulating material thereof and a method for preparing the encapsulating material. The method for encapsulating the all-solid thin film lithium ion battery takes the all-solid thin film lithium ion battery to be encapsulated as a substrate, and a silicon nitrogen compound layer with the thickness of 30-500nm and a silicon dioxide compound layer with the thickness of 30-500nm are sequentially formed on the external surface of the substrate through a radio frequency magnetron sputtering method. The encapsulating material is the thin film which is formed by the silicon nitrogen compound layer with the thickness of 30-500nm and the silicon dioxide compound layer with the thickness of 30-500nm; and the method for preparing the encapsulating material is as the same as the method for encapsulating the battery. The method for encapsulating the all-solid thin film lithium ion battery, the encapsulating material thereof and the method for preparing the encapsulating material are used for overcoming the defects that the all-solid thin film lithium ion battery has low encapsulating layer density, poor environmental stability and the like in the prior art.
Description
Technical field
the present invention relates to the encapsulation technology of solid-State Thin Film Li-Ion Batteries, be specifically related to solid-State Thin Film Li-Ion Batteries method, the encapsulating material that the method adopts and the preparation method of encapsulating material.
Background technology
development along with electronics industry; at present a lot of microelectronic devices need micro power that can integrated low current output; for example, miniature transplantation medicine equipment (rhythm of the heart adjuster, nerve stimulator and drug delivery), the integrated circuit based on CMOS, bank's antitheft tracing system, electronic anti-theft protection, mini type gas sensor, miniature Coulomb meter, " intelligence " safety card, power is wireless asset tracking sign, electronical record tracking system and other micromodule equipment all need ultra-thin, light, high-energy power supply.
solid-State Thin Film Li-Ion Batteries is the latest fields of lithium ion battery development, its thickness can reach even micron order of millimeter, lightweight except having, capacity density is high, the life-span is long, antidetonation, resistance to collision and the advantage such as volume is little, also have the following advantages: (1) can be designed to arbitrary shape according to the requirement of product; (2) can be assembled in the substrate of different materials; (3) sedimentary condition of available standards realizes the preparation of hull cell; (4) working temperature window wide (15 ~ 150 ℃); (5) there is no solid-liquid contact interface, reduced solid liquid interface resistance; (6) when battery operated, there is no gaseous product, coefficient of safety is high.The above-mentioned advantage that solid-State Thin Film Li-Ion Batteries has becomes the ideal source of microelectronic component.
in the production of solid-State Thin Film Li-Ion Batteries, encapsulation is to determine battery rate of finished products and the important step in life-span, when encapsulation, needs to guarantee battery abundant performance of controlling steam and oxygen molecule transit dose on the film of several microns.Prior art is to be coated with one deck macromolecule glue at battery surface for the method for packing of solid-State Thin Film Li-Ion Batteries, and the density of gained encapsulated layer is little, and encapsulation performance is not ideal enough, and poor stability.
Summary of the invention
technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of method for packing of new solid-State Thin Film Li-Ion Batteries is provided, and the density of gained encapsulated layer is high, environmental stability good.
the present invention also will provide the solid-State Thin Film Li-Ion Batteries encapsulating material that a kind of density is high, environmental stability is good simultaneously.
the present invention also will provide a kind of solid-State Thin Film Li-Ion Batteries preparation method with encapsulating material simultaneously, high by its gained encapsulating material density, environmental stability good.
for solving above technical problem, a kind of technical scheme that the present invention takes is:
a kind of method for packing of solid-State Thin Film Li-Ion Batteries, this method for packing is to take solid-State Thin Film Li-Ion Batteries to be packaged as substrate, by radio frequency magnetron sputtering method, at its outer surface, forms successively the silicon oxide compound layer that silicon-nitrogen compound layer that thickness is 30 ~ 500nm and thickness are 30 ~ 500nm.
according to further of the present invention and preferred version: described method for packing specifically comprises the steps:
1., the purity of usining is more than or equal to 99.999% HIGH-PURITY SILICON as target, take solid-State Thin Film Li-Ion Batteries to be packaged as substrate, installs after target and substrate, closes sputtering chamber, and sputtering chamber is evacuated to 1.0 * 10
-4
pa or following, be filled with 1 atmospheric by helium and the nitrogen mist that 0.2 ~ 1:1 forms by volume, then indoor gas pressure is evacuated to 0.1 ~ 3Pa;
2., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
3., setting sputtering power scope is 1W/cm
2
~ 6W/cm
2
, target-substrate distance is from being 40mm ~ 100mm, sputtering time is 2 ~ 10 hours, forms the described silicon-nitrogen compound layer of film-form;
4., sputtering chamber is evacuated to 1.0 * 10
-4
pa or following, is filled with 1 atmospheric helium and the oxygen mist that 0.2 ~ 1:1 forms by volume, then indoor gas pressure is evacuated to 0.1 ~ 3Pa;
5., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
6., setting sputtering power scope is 1W/cm
2
~ 6W/cm
2
, target-substrate distance is from being 40mm ~ 100mm, sputtering time is 2 ~ 10 hours, forms the described silicon oxide compound layer of film-form.
preferably, in sputter procedure, controlling substrate temperature is 120 ~ 350 ℃.Substrate is controlled at this temperature, can obtains good silicon-nitrogen compound layer and silicon oxide compound layer, improve the reliability of micro cell.
preferably, step 1. in, described HIGH-PURITY SILICON is made by powder metallurgy process.
preferably, step 1. in, the grain size of described HIGH-PURITY SILICON is 10 ~ 15 μ m, relative density is more than or equal to 99%, diameter is 55 ~ 65mm.
the another technical scheme that the present invention takes is: a kind of solid-State Thin Film Li-Ion Batteries encapsulating material, it is that silicon-nitrogen compound layer and thin film silicon nitrogen compound layer and the silicon oxide compound layer that is formed on the silicon oxide compound layer formation on silicon-nitrogen compound layer all form by radio frequency magnetron sputtering method, and the thickness of the two is 30 ~ 500nm independently.
further, described encapsulating material prepares as follows:
1., the purity of usining is more than or equal to 99.999% HIGH-PURITY SILICON as target, take solid-State Thin Film Li-Ion Batteries to be packaged as substrate, installs after target and substrate, closes sputtering chamber, and sputtering chamber is evacuated to 1.0 * 10
-4
pa or following, be filled with 1 atmospheric by helium and the nitrogen mist that 0.2 ~ 1:1 forms by volume, then indoor gas pressure is evacuated to 0.1 ~ 3Pa;
2., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
3., setting sputtering power scope is 1W/cm
2
~ 6W/cm
2
, target-substrate distance is from being 40mm ~ 100mm, sputtering time is 2 ~ 10 hours, forms the described silicon-nitrogen compound layer of film-form;
4., sputtering chamber is evacuated to 1.0 * 10
-4
pa or following, is filled with 1 atmospheric helium and the oxygen mist that 0.2 ~ 1:1 forms by volume, then indoor gas pressure is evacuated to 0.1 ~ 3Pa;
5., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
6., setting sputtering power scope is 1W/cm
2
~ 6W/cm
2
, target-substrate distance is from being 40mm ~ 100mm, sputtering time is 2 ~ 10 hours, forms the described silicon oxide compound layer of film-form.
preferably, step 1. in, described HIGH-PURITY SILICON is made by powder metallurgy process.
preferably, step 1. in, the grain size of described HIGH-PURITY SILICON is 10 ~ 15 μ m, relative density is more than or equal to 99%.
the another technical scheme that the present invention takes is: the preparation method of encapsulating material for a kind of above-mentioned solid-State Thin Film Li-Ion Batteries, it comprises the steps:
1., the purity of usining is more than or equal to 99.999% HIGH-PURITY SILICON as target, take solid-State Thin Film Li-Ion Batteries to be packaged as substrate, installs after target and substrate, closes sputtering chamber, and sputtering chamber is evacuated to 1.0 * 10
-4
pa or following, be filled with 1 atmospheric by helium and the nitrogen mist that 0.2 ~ 1:1 forms by volume, then indoor gas pressure is evacuated to 0.1 ~ 3Pa;
2., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
3., setting sputtering power scope is 1W/cm
2
~ 6W/cm
2
, target-substrate distance is from being 40mm ~ 100mm, sputtering time is 2 ~ 10 hours, forms the described silicon-nitrogen compound layer of film-form;
4., sputtering chamber is evacuated to 1.0 * 10
-4
pa or following, is filled with 1 atmospheric helium and the oxygen mist that 0.2 ~ 1:1 forms by volume, then indoor gas pressure is evacuated to 0.1 ~ 3Pa;
5., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
6., setting sputtering power scope is 1W/cm
2
~ 6W/cm
2
, target-substrate distance is from being 40mm ~ 100mm, sputtering time is 2 ~ 10 hours, forms the described silicon oxide compound layer of film-form.
preferably, step 1. in, described HIGH-PURITY SILICON is made by powder metallurgy process.
preferably, step 1. in, the grain size of described HIGH-PURITY SILICON is 10 ~ 15 μ m, relative density is more than or equal to 99%.
preferably, in sputter procedure, controlling substrate temperature is 120 ~ 350 ℃.Substrate is controlled at this temperature, can obtains good silicon-nitrogen compound layer and silicon oxide compound layer, improve the reliability of micro cell.
due to the utilization of technique scheme, the present invention compared with prior art has following advantages and effect:
method for packing provided by the invention is simple, convenient, between formed encapsulated layer and battery surface, adhesion is strong, the density of encapsulated layer own is high, environmental stability good, contributes to improve the dependability of solid-State Thin Film Li-Ion Batteries and extend its life-span.
encapsulating material provided by the invention can guarantee that battery is in the process of repeated charge, without moisture, sees through encapsulated layer, and the phenomenons such as adhesion is little, peel off do not appear in encapsulated layer, is the desirable encapsulated layer material of a kind of desirable solid-State Thin Film Li-Ion Batteries.
the preparation method of encapsulating material provided by the invention, is directly in solid-State Thin Film Li-Ion Batteries, to form encapsulated layer, also completes the method for encapsulation, has the advantages such as simple to operate, convenient and gained encapsulating material density is high, environmental stability is good.
Accompanying drawing explanation
fig. 1 is the scanning electron microscope (SEM) photograph on the formed silicon-nitrogen compound layer of embodiment 1 surface;
fig. 2 is the scanning electron microscope (SEM) photograph of the formed silicon-nitrogen compound layer of embodiment 1 on thickness direction;
fig. 3 is the scanning electron microscope (SEM) photograph of the formed silicon oxide compound layer of embodiment 1;
fig. 4 is embodiment 1 acquisition encapsulating material is at the scanning electron microscope (SEM) photograph of thickness direction.
Embodiment
below in conjunction with accompanying drawing and specific embodiment, the present invention will be further described in detail, but the invention is not restricted to following examples.
embodiment 1
the present embodiment provides a kind of method for packing (or solid-State Thin Film Li-Ion Batteries preparation method of encapsulating material) of solid-State Thin Film Li-Ion Batteries, and it specifically comprises the steps:
1., with HIGH-PURITY SILICON, (adopt the method for powder metallurgy to make, 10 ~ 15 microns of grain sizes, relative density is greater than 99%, purity is greater than 99.999%, diameter is 60mm) as target, take solid-State Thin Film Li-Ion Batteries to be packaged as substrate, install after target and substrate, close sputtering chamber, sputtering chamber is evacuated to 1.0 * 10
-4
pa, be filled with 1 atmospheric by helium and the nitrogen mist that 0.3:1 forms by volume, then indoor gas pressure is evacuated to 0.5Pa;
2., pre-sputtering 15min, to clear up oxide layer and the impurity of target material surface;
3., setting sputtering power scope is 3W/cm
2
, target-substrate distance is from being 60mm, sputtering time is 5 hours, forms the silicon-nitrogen compound layer (SiNx) of film-form;
4., sputtering chamber is evacuated to 1.0 * 10
-4
pa, is filled with 1 atmospheric helium and the oxygen mist that 0.4:1 forms by volume, then indoor gas pressure is evacuated to 1.2Pa;
5., pre-sputtering 15min, to clear up oxide layer and the impurity of target material surface;
6., setting sputtering power scope is 3W/cm
2
, target-substrate distance is from being 60mm, sputtering time is 5 hours, forms the silicon oxide compound layer (SiOx) of film-form;
7. close sputtering equipment, treat that substrate is cooled to room temperature, substrate is taken out, measure.
referring to Fig. 1 to Fig. 4, visible, the prepared encapsulating material (encapsulated layer) forming on solid-State Thin Film Li-Ion Batteries surface of the present embodiment is the bilayer film of SiNx/SiOx structure, and the thickness of SiNx layer and SiOx layer is about 315nm and 267nm respectively.The density on SiNx layer and SiOx layer surface is very high, can effectively control the transit dose of steam and oxygen molecule.In addition,, with comparing of the formed encapsulated layer of existing painting macromolecule glue, the formed encapsulated layer environmental stability of the present invention has significant advantage.
embodiment 2
the present embodiment provides a kind of method for packing (or solid-State Thin Film Li-Ion Batteries preparation method of encapsulating material) of solid-State Thin Film Li-Ion Batteries, and it specifically comprises the steps:
1., with HIGH-PURITY SILICON, (adopt the method for powder metallurgy to make, 10 ~ 15 microns of grain sizes, relative density is greater than 99%, purity is greater than 99.999%, diameter is 60mm) as target, take solid-State Thin Film Li-Ion Batteries to be packaged as substrate, install after target and substrate, close sputtering chamber, sputtering chamber is evacuated to 1.0 * 10
-4
pa, be filled with 1 atmospheric by helium and the nitrogen mist that 1:1 forms by volume, then indoor gas pressure is evacuated to 0.5Pa;
2., pre-sputtering 15min, to clear up oxide layer and the impurity of target material surface;
3., setting sputtering power scope is 1.5W/cm
2
, target-substrate distance is from being 50mm, sputtering time is 3 hours, forms the silicon-nitrogen compound layer (SiNx) of film-form;
4., sputtering chamber is evacuated to 1.0 * 10
-4
pa, is filled with 1 atmospheric helium and the oxygen mist that 0.2:1 forms by volume, then indoor gas pressure is evacuated to 1.2Pa;
5., pre-sputtering 15min, to clear up oxide layer and the impurity of target material surface;
6., setting sputtering power scope is 1.5W/cm
2
, target-substrate distance is from being 50mm, sputtering time is 3 hours, forms the silicon oxide compound layer (SiOx) of film-form;
7. close sputtering equipment, treat that substrate is cooled to room temperature, substrate is taken out, measure.
equally, by scanning electron microscopy (SEM), observe and measure the thickness of encapsulating material and observe surface compact.Result shows, encapsulated layer prepared by the present embodiment is the bilayer film of SiNx/SiOx structure, and the thickness of SiNx layer and SiOx layer is about 61nm and 47nm respectively.The density on SiNx layer and SiOx layer surface is very high.
embodiment 3
the present embodiment provides a kind of method for packing (or solid-State Thin Film Li-Ion Batteries preparation method of encapsulating material) of solid-State Thin Film Li-Ion Batteries, and it specifically comprises the steps:
1., with HIGH-PURITY SILICON, (adopt the method for powder metallurgy to make, 10 ~ 15 microns of grain sizes, relative density is greater than 99%, purity is greater than 99.999%, diameter is 60mm) as target, take solid-State Thin Film Li-Ion Batteries to be packaged as substrate, install after target and substrate, close sputtering chamber, sputtering chamber is evacuated to 1.0 * 10
-4
pa, be filled with 1 atmospheric by helium and the nitrogen mist that 0.5:1 forms by volume, then indoor gas pressure is evacuated to 0.5Pa;
2., pre-sputtering 15min, to clear up oxide layer and the impurity of target material surface;
3., setting sputtering power scope is 5W/cm
2
, target-substrate distance is from being 80mm, sputtering time is 6 hours, forms the silicon-nitrogen compound layer (SiNx) of film-form;
4., sputtering chamber is evacuated to 1.0 * 10
-4
pa, is filled with 1 atmospheric helium and the oxygen mist that 1:1 forms by volume, then indoor gas pressure is evacuated to 1.2Pa;
5., pre-sputtering 15min, to clear up oxide layer and the impurity of target material surface;
6., setting sputtering power scope is 5W/cm
2
, target-substrate distance is from being 80mm, sputtering time is 6 hours, forms the silicon oxide compound layer (SiOx) of film-form;
7. close sputtering equipment, treat that substrate is cooled to room temperature, substrate is taken out, measure.
equally, by scanning electron microscopy (SEM), observe and measure the thickness of encapsulating material and observe surface compact.Result shows, encapsulated layer prepared by the present embodiment is the bilayer film of SiNx/SiOx structure, and the thickness of SiNx layer and SiOx layer is about 419nm and 388nm respectively.The density on SiNx layer and SiOx layer surface is very high.
above-described embodiment is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that Spirit Essence is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. the method for packing of a solid-State Thin Film Li-Ion Batteries, it is characterized in that: described method for packing is to take solid-State Thin Film Li-Ion Batteries to be packaged as substrate, by radio frequency magnetron sputtering method, at its outer surface, form successively the silicon oxide compound layer that silicon-nitrogen compound layer that thickness is 30~500nm and thickness are 30~500nm.
2. the method for packing of solid-State Thin Film Li-Ion Batteries according to claim 1, is characterized in that: described method for packing specifically comprises the steps:
1., the purity of usining is more than or equal to 99.999% HIGH-PURITY SILICON as target, take solid-State Thin Film Li-Ion Batteries to be packaged as substrate, installs after target and substrate, closes sputtering chamber, and sputtering chamber is evacuated to 1.0 * 10
-4pa or following, be filled with 1 atmospheric by helium and the nitrogen mist that 0.2~1:1 forms by volume, then indoor gas pressure is evacuated to 0.1~3Pa;
2., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
3., setting sputtering power scope is 1W/cm
2~6W/cm
2, target-substrate distance is from being 40mm~100mm, sputtering time is 2~10 hours, forms the described silicon-nitrogen compound layer of film-form;
4., sputtering chamber is evacuated to 1.0 * 10
-4pa or following, is filled with 1 atmospheric helium and the oxygen mist that 0.2~1:1 forms by volume, then indoor gas pressure is evacuated to 0.1~3Pa;
5., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
6., setting sputtering power scope is 1W/cm
2~6W/cm
2, target-substrate distance is from being 40mm~100mm, sputtering time is 2~10 hours, forms the described silicon oxide compound layer of film-form.
3. the method for packing of solid-State Thin Film Li-Ion Batteries according to claim 2, is characterized in that: in sputter procedure, controlling substrate temperature is 120~350 ℃.
4. a solid-State Thin Film Li-Ion Batteries encapsulating material, it is characterized in that: described encapsulating material is silicon-nitrogen compound layer and is formed on the film that the silicon oxide compound layer on described silicon-nitrogen compound layer forms, described silicon-nitrogen compound layer and described silicon oxide compound layer all form by radio frequency magnetron sputtering method, and the thickness of the two is 30~500nm independently.
5. solid-State Thin Film Li-Ion Batteries encapsulating material according to claim 4, is characterized in that: described encapsulating material prepares as follows:
1., the purity of usining is more than or equal to 99.999% HIGH-PURITY SILICON as target, take solid-State Thin Film Li-Ion Batteries to be packaged as substrate, installs after target and substrate, closes sputtering chamber, and sputtering chamber is evacuated to 1.0 * 10
-4pa or following, be filled with 1 atmospheric by helium and the nitrogen mist that 0.2~1:1 forms by volume, then indoor gas pressure is evacuated to 0.1~3Pa;
2., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
3., setting sputtering power scope is 1W/cm
2~6W/cm
2, target-substrate distance is from being 40mm~100mm, sputtering time is 2~10 hours, forms the described silicon-nitrogen compound layer of film-form;
4., sputtering chamber is evacuated to 1.0 * 10
-4pa or following, is filled with 1 atmospheric helium and the oxygen mist that 0.2~1:1 forms by volume, then indoor gas pressure is evacuated to 0.1~3Pa;
5., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
6., setting sputtering power scope is 1W/cm
2~6W/cm
2, target-substrate distance is from being 40mm~100mm, sputtering time is 2~10 hours, forms the described silicon oxide compound layer of film-form.
6. solid-State Thin Film Li-Ion Batteries encapsulating material according to claim 5, is characterized in that: step 1. in, described HIGH-PURITY SILICON is made by powder metallurgy process.
7. according to the solid-State Thin Film Li-Ion Batteries encapsulating material described in claim 5 or 6, it is characterized in that: step 1. in, the grain size of described HIGH-PURITY SILICON is 10~15 μ m, relative density is more than or equal to 99%.
8. a preparation method for encapsulating material for solid-State Thin Film Li-Ion Batteries as claimed in claim 4, is characterized in that: comprise the steps:
1., the purity of usining is more than or equal to 99.999% HIGH-PURITY SILICON as target, take solid-State Thin Film Li-Ion Batteries to be packaged as substrate, installs after target and substrate, closes sputtering chamber, and sputtering chamber is evacuated to 1.0 * 10
-4pa or following, be filled with 1 atmospheric by helium and the nitrogen mist that 0.2~1:1 forms by volume, then indoor gas pressure is evacuated to 0.1~3Pa;
2., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
3., setting sputtering power scope is 1W/cm
2~6W/cm
2, target-substrate distance is from being 40mm~100mm, sputtering time is 2~10 hours, forms the described silicon-nitrogen compound layer of film-form;
4., sputtering chamber is evacuated to 1.0 * 10
-4pa or following, is filled with 1 atmospheric helium and the oxygen mist that 0.2~1:1 forms by volume, then indoor gas pressure is evacuated to 0.1~3Pa;
5., pre-sputtering, to clear up oxide layer and the impurity of target material surface;
6., setting sputtering power scope is 1W/cm
2~6W/cm
2, target-substrate distance is from being 40mm~100mm, sputtering time is 2~10 hours, forms the described silicon oxide compound layer of film-form.
9. the preparation method of encapsulating material for solid-State Thin Film Li-Ion Batteries according to claim 8, is characterized in that: step 1. in, the grain size of described HIGH-PURITY SILICON is 10~15 μ m, relative density is more than or equal to 99%.
10. the preparation method of encapsulating material for solid-State Thin Film Li-Ion Batteries according to claim 8, is characterized in that: in sputter procedure, controlling substrate temperature is 120~350 ℃.
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CN1883076A (en) * | 2003-11-14 | 2006-12-20 | 原子能委员会 | lithium microbattery provided with a protective envelope, and method for producing one such microbattery |
CN1945881A (en) * | 2006-11-02 | 2007-04-11 | 复旦大学 | Full solid thin film lithium battery and its producing method |
CN102315398A (en) * | 2011-09-29 | 2012-01-11 | 万海电源(烟台)有限公司 | Packaging method of lithium ion battery |
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CN1883076A (en) * | 2003-11-14 | 2006-12-20 | 原子能委员会 | lithium microbattery provided with a protective envelope, and method for producing one such microbattery |
CN1945881A (en) * | 2006-11-02 | 2007-04-11 | 复旦大学 | Full solid thin film lithium battery and its producing method |
CN102315398A (en) * | 2011-09-29 | 2012-01-11 | 万海电源(烟台)有限公司 | Packaging method of lithium ion battery |
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