CN103137917A - Battery sealing assembly and production method thereof, and lithium ion battery - Google Patents
Battery sealing assembly and production method thereof, and lithium ion battery Download PDFInfo
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- CN103137917A CN103137917A CN201110379551XA CN201110379551A CN103137917A CN 103137917 A CN103137917 A CN 103137917A CN 201110379551X A CN201110379551X A CN 201110379551XA CN 201110379551 A CN201110379551 A CN 201110379551A CN 103137917 A CN103137917 A CN 103137917A
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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
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Abstract
The present invention relates to a battery sealing assembly and a production method thereof. The battery sealing assembly comprises: a ceramic ring, a metal ring and a core column, wherein an inner hole is formed on the middle portion of the ceramic ring, the metal ring is connected with the outer side of the ceramic ring, and the core column is connected into the inner hole of the ceramic ring and is a titanium core column or a titanium alloy core column. The production method comprises the following steps: connecting the titanium core column or the titanium alloy core column into the inner hole of the ceramic ring, and connecting the metal ring to the outer side of the ceramic ring to obtain the battery sealing assembly. The present invention further provides a lithium ion battery adopting the battery sealing assembly. According to the present invention, the titanium or the titanium alloy is adopted as the core column, the titanium base welding material is adopted to weld the core column and the ceramic ring, and the titanium base welding material layer does not contain components capable of generating lithium embedding and lithium removing, and has strong electrochemical corrosion resistance, such that the battery sealing assembly has a long service life.
Description
Technical field
The present invention relates to the technical field of sealing technology of battery; Particularly, the present invention relates to a kind of black box and preparation method thereof and a kind of lithium ion battery of battery.
Background technology
At present, in the packaging technology of battery commonly used, can be divided into Plastic Package, glass packaging and ceramic packaging three major types according to encapsulating material; Wherein, plastics connect from angle consideration in useful life, the more difficult instructions for use of satisfying the long-life (more than 20 years) energy-storage battery and reliability electrokinetic cell.In the sealing of existing lithium ion battery, it is to connect by vitreum that the cover plate of black box is connected with stem stem.For example: CN2419690 discloses a kind of lid of lithium ion battery.Battery case cover plate and electrode draw core and admittedly seal with vitreum; Have liquid injection hole on the battery case cover plate, liquid injection hole is with safe valve block sealing.Battery case, vitreum and electrode draw the temperature coefficient of core and answer identical or close.The sealing of battery and the release of dangerous pressure be can guarantee, thereby efficient and the security performance of lithium ion battery improved.
But after lithium ion battery used for a long time and stores, the vitreum lower floor that directly contacts with the electrolyte of lithium ion battery can be corroded.For example: French SAFT company carries out anticorrosive test by the accelerated aging test method to vitreum, after black box and lithium ion battery body are assembled into lithium ion battery, placed 7 days under 150 ℃, found that vitreous surface is corroded, the air-tightness of black box reduces, less than 1.0 * 10
-7m
3Pa/s.Producing this existing main cause is: lithium metal can be gone back the silicon dioxide in bare glass, and can constantly penetrate in vitreum, not only reduces the insulation property of glass, more can cause the leakage of lithium battery.At present, solve problems abroad mainly by the not silica containing corrosion resistance insulating glass of exploitation, and the connection temperature of this glass is higher, all very harsh to the requirement of equipment and process conditions.
Thereby ceramic seal becomes the direction of those skilled in the art's primary study, those skilled in the art will appreciate that existing battery adopts aluminium and copper material respectively as the material of the positive and negative electrode stem stem of battery mostly.But pottery must use activated solder as weld layer, for example with metallic aluminium, when copper is connected: pottery needs Al-Si or Al-Si-Mg activated solder when welding with metallic aluminium; Si when battery charging and discharging can with electrolyte in lithium ion generation embedding lithium take off lithium reaction, containing the Si weld layer can lose efficacy because being corroded, and causes battery leakage; When pottery and metallic copper weld, need to use Ag base, Au parent metal, these two kinds of scolders not only price are extremely expensive, and Ag parent metal layer can be subjected to the electrolyte corrosion failure when battery charging and discharging, cause battery leakage, be difficult to satisfy the requirement of long service life.
Summary of the invention
The present invention adopts aluminium and copper material as the material of the positive and negative electrode stem stem of battery for the black box that solves battery of the prior art, then adopt pottery to use activated solder as weld layer with metallic aluminium, when copper is connected, the activated solder that adopts can lose efficacy because being subjected to the electrolyte corrosion, cause battery leakage, be difficult to satisfy the technical problem of the requirement of long service life.
In order to solve the problems of the technologies described above, the invention provides a kind of black box of battery, comprise: ceramic ring, becket and stem stem, the middle part of described ceramic ring is formed with endoporus, described becket is connected in outside described ceramic ring, described stem stem is connected in the endoporus of described ceramic ring, and described stem stem is the stem stem of titanium or titanium alloy, is provided with titanium parent metal layer between the stem stem of described titanium or titanium alloy and described ceramic ring.
In the black box of described battery, preferably, described titanium alloy is selected from a kind of in titanium-aluminium alloy, titanium maxter alloy, titanium palldium alloy, ferro-titanium, Ti-Ni alloy.
In the black box of described battery, preferably, described titanium parent metal comprises Ti, and comprises one or more in Zr, Ni, Cu.
In the black box of described battery, preferably, described ceramic ring is a kind of in the compound ceramic ring of aluminium oxide ceramics ring, zirconia ceramics ring, alumina zirconia.
In the black box of described battery, preferably, described becket is the aluminum or aluminum alloy ring.
In the black box of described battery, preferably, also be provided with aluminium base solder layer between described becket and described ceramic ring, described aluminium base scolder comprises Al, and comprises one or both in Si, Mg.
The present invention also provides the manufacture method of the black box of above-mentioned battery, comprises the steps:
Step 1: the stem stem of titanium or titanium alloy is connected in the endoporus of ceramic ring;
Step 2: becket is connected in the outside of ceramic ring, obtains the black box of described battery.
In described manufacture method, preferably, in step 1, the stem stem of titanium or titanium alloy is installed in the endoporus of ceramic ring, then adopt welding procedure that the stem stem of described titanium or the titanium alloy inner hole wall with ceramic ring is welded mutually; The scolder that described welding procedure adopts is the titanium parent metal, and the condition of welding procedure: under vacuum atmosphere, welding temperature is 830-900 ℃, and be 3-15 minute weld time.
In described manufacture method, preferably, in step 2, described becket adopts soldering processes to be connected in the outside of ceramic ring; The scolder that described soldering processes adopt is aluminium base scolder, and described aluminium base scolder comprises Al, and comprises one or both in Si, Mg; The condition of soldering processes: brazing temperature is 570-660 ℃, and the holding time is 3-15 minute, and atmosphere is vacuum or inert gas atmosphere.
The present invention further provides a kind of lithium ion battery, comprise: the housing of at least one end opening, be sealed in the black box of the openend of described housing, form seal cavity between described housing and black box, contain pole piece and electrolyte in described seal cavity, described black box adopts the black box of battery as above, wherein, described becket is connected with housing, and the stem stem of described titanium or titanium alloy is connected with described pole piece.
The present invention adopts titanium or titanium alloy as stem stem, and adopt the titanium parent metal that described stem stem and ceramic ring are welded, described titanium parent metal layer does not contain the composition that the embedding lithium can occur, take off lithium, have very strong advantage aspect electrochemical corrosion resistant, make the black box of battery of the present invention have longer useful life.And have the close coefficient of expansion between the stem stem of described titanium or titanium alloy and ceramic ring, the cold-hot impact property is better, and cost is lower, is fit to produce in enormous quantities; Compare with existing black box, black box of the present invention can be good at satisfying the requirement that battery connects long-life and stability.
Description of drawings
Fig. 1 is the schematic diagram of the black box of battery of the present invention.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
With reference to the accompanying drawings the specific embodiment of the present invention is elaborated.Herein, same reference numerals represents the same composition part.
The black box of battery of the present invention is used for the sealing of battery, is used for more sealing, the especially high-power lithium ion battery of lithium ion battery, for example: the sealing of lithium-ion-power cell, lithium-ion energy storage battery.Skilled in the art will recognize that lithium ion battery mainly comprises: the housing of at least one end opening, be positioned over the pole piece in housing and be contained in electrolyte in housing.For fear of spilling of electrolyte, adopt black box that the openend of housing is sealed.Wherein, described housing is generally aluminum hull or box hat, is used for placing pole piece and holds electrolyte, its at least one end opening.Described pole piece is formed by positive plate, barrier film, negative plate stacked or coiling successively, and the structure of pole piece and manufacture method can be passed through existing techniques in realizing, do not do at this and give unnecessary details.
Improvements of the present utility model mainly are black box, as shown in Figure 1, the black box of battery of the present invention, comprise: ceramic ring 2, stem stem 3, becket 1, becket 1 is connected in the outside of described ceramic ring 2, ceramic ring 2 is formed with endoporus, and stem stem 3 is arranged in described endoporus, and is connected with described endoporus; In the present invention, described stem stem 3 is the stem stem of titanium or titanium alloy, and is provided with titanium parent metal layer 4 between the stem stem of described titanium or titanium alloy and described ceramic ring, is connected with the inside of described ceramic ring 2 with the stem stem with described titanium or titanium alloy.
Existing battery adopts aluminium and copper material respectively as the material of the positive and negative electrode stem stem of battery mostly, but, pottery must use activated solder as weld layer with metallic aluminium, when copper is connected, pottery need to adopt Al-Si or Al-Si-Mg activated solder when welding with metallic aluminium, when pottery welds with metallic copper, need to use Ag base, Au parent metal, these scolders when battery charging and discharging can with electrolyte in lithium ion generation embedding lithium take off lithium reaction, be subjected to the electrolyte corrosion failure, cause battery leakage, be difficult to satisfy the requirement of long service life.The present inventor is in the process that studies for a long period of time to battery, unexpected discovery can adopt titanium or titanium alloy as the material of the positive and negative electrode stem stem of battery, and adopt the titanium parent metal that stem stem and the pottery of titanium or titanium alloy are welded, this titanium parent metal does not contain the composition that the embedding lithium can occur, take off lithium, have very strong advantage aspect electrochemical corrosion resistant, make the black box of battery of the present invention have longer useful life.
Specifically, described becket 1 is aluminium ring or aluminum alloy ring, for example: adopt 3003 aluminum alloy rings.Becket 1 welds mutually with the housing of lithium ion battery, so that the openend of black box seal casinghousing; Certainly, described becket 1 can also for other becket of the identical material of housing, for example: steel loop, becket 1 is used for being connected with the housing of lithium ion battery (generally realizing being connected by welding), to realize being tightly connected of whole black box of the present invention and lithium-ion electric tank main body.The middle part of described becket 1 forms installing hole, and the aperture of installing hole equals the external diameter of ceramic ring 2, is used for connecting ceramic ring 2.Becket 1 is connected with housing, thereby need to guarantee that stem stem 3 insulate mutually with becket 1, in the present invention, by the setting of ceramic ring 2, stem stem 3 is connected with becket 1 and guarantees insulation between them.described becket 1 welds by aluminium base scolder with described ceramic ring 2, thereby be formed with aluminium base solder layer 5 between described becket 1 and described ceramic ring 2, described aluminium base scolder can be the Al-Si scolder, Al-Mg scolder or Al-Si-Mg scolder, becket 1 has been conventionally known to one of skill in the art with the welding of ceramic ring 2 and the aluminium base scolder of employing thereof, need to prove, although also contain Si in the aluminium base solder layer 5 between becket 1 and ceramic ring 2, but due to aluminium base solder layer 5 can be when the battery charging and discharging and the lithium ion generation embedding lithium in electrolyte take off the lithium reaction, it is in zero potential always, thereby require not weld scolder strict of stem stem and ceramic ring.
Main improvements of the present invention are stem stem 3, stem stem of the present invention is the stem stem of titanium or titanium alloy, adopting pure titanium or titanium alloy to make forms, described titanium alloy can be selected conventional titanium alloy, for example is selected from a kind of in titanium-aluminium alloy, titanium maxter alloy, titanium palldium alloy, ferro-titanium, Ti-Ni alloy.Because the thermal coefficient of expansion (8-10 ppm/K) of titanium or titanium alloy is less compared to the thermal coefficient of expansion of aluminum or aluminum alloy, copper or copper alloy, for example: the thermalexpansioncoefficientα of fine aluminium
2=23.2ppm/K.The present invention adopts the stem stem of titanium or titanium alloy, can overcome the difference of the thermal coefficient of expansion between ceramic ring and stem stem, makes the thermal coefficient of expansion of stem stem and ceramic ring be complementary.What is more important, described stem stem is the stem stem of titanium or titanium alloy, makes the welding of stem stem and ceramic ring can adopt the titanium parent metal to weld, described titanium parent metal comprises Ti, and comprises one or more in Zr, Ni, Cu; Described titanium parent metal layer 4 does not contain lithium ion generation embedding lithium when battery charging and discharging and in electrolyte, takes off the composition of lithium, thereby has very strong advantage aspect electrochemical corrosion resistant, makes the black box of battery of the present invention have longer useful life.
In the present invention, the upper/lower terminal of described stem stem 3 exposes described ceramic ring 2, and the upper end of stem stem 3 is exposed ceramic ring 2 and be can be used for negative pole or negative pole exit, external power consumption equipment; Ceramic ring 2 is exposed in its lower end, is used for being electrically connected with the pole piece of lithium ion battery, to realize the inside and outside electrical connection of lithium ion battery.
The invention provides the manufacture method of the black box of above-mentioned battery, comprise the steps:
when the black box of above-mentioned battery is used for assembling whole lithium ion battery, for example: with the housing of lithium ion battery as positive pole, be example with the stem stem of black box as negative pole, black box is the black box of battery cathode, one end opening of housing, pole piece is positioned in housing, and fluid injection in the housing (is perhaps follow-uply carried out fluid injection by the liquid injection hole on becket, known to those skilled in the art), then black box is installed on this openend of housing, in this process, the becket of black box is welded mutually with housing, and the stem stem of black box is connected with pole piece, after installation, form seal cavity between black box and housing, contain pole piece and electrolyte in the sealing space, housing and stem stem are respectively as the two poles of the earth of lithium ion battery, can external power consumption equipment.
again for example: with the equal opening in the two ends of housing, black box is installed respectively, wherein a black box is the black box of anode, and the black box that another black box is battery cathode is example, these two black boies are installed on respectively two openends of housing, in this process, the becket of these two black boies is welded mutually with housing, and the stem stem of these two black boies is connected with pole piece, after installation, form seal cavity between these two black boies and housing, contain pole piece and electrolyte in the sealing space, the stem stem of these two black boies is respectively as the two poles of the earth of lithium ion battery, external power consumption equipment.
In sum, the present invention has following characteristics: the present invention adopts titanium or titanium alloy as stem stem, and adopt the titanium parent metal that described stem stem and ceramic ring are welded, described titanium parent metal layer does not contain the composition that the embedding lithium can occur, take off lithium, have very strong advantage aspect electrochemical corrosion resistant, make the black box of battery of the present invention have longer useful life.And have the close coefficient of expansion between the stem stem of described titanium or titanium alloy and ceramic ring, the cold-hot impact property is better, and the connection of whole black box is reliable.In addition, the cost of titanium or titanium alloy stem stem is lower, is fit to produce in enormous quantities; Compare with existing black box, black box of the present invention can be good at satisfying the requirement that battery connects long-life and stability.
The present invention is further illustrated below by embodiment.
The present embodiment is used for illustrating black box of battery disclosed by the invention and preparation method thereof;
Embodiment 4
Comparative Examples 1
Comparative Examples 1 is used for the making of the black box of the existing battery of explanation;
Adopt the method for crunch seal, under vacuum condition, the stem stem employing Al parent metal that ceramic ring and metallic aluminium, copper are done welds together, and weld metal ring then is made into the black box D1 of anode; Adopt Ag base, Au parent metal to weld together the stem stem of ceramic ring and metallic copper making, then the weld metal ring is made into the black box D2 of battery cathode.
Performance test
the black box A1-A4 of the battery that embodiment 1-4 is made and the black box D1 of the battery that Comparative Examples 1 makes, D2 tests, place 3min in the cold water below 0 ℃, be transferred to immediately in the boiling water more than 100 ℃ and be incubated 3min, repeat this process, the test black box is after completing the how many times circulation, still can pass through air tightness test, the process of air tightness test is: the connecting portion of black box to be tested is exposed the clips chamber, fill 0.6MPa pressure in cavity, pressurize 3min, drip at connecting portion simultaneously, if bubbling, be considered as gas leakage, if there is no the bubbling phenomenon, being considered as air-tightness meets the demands, test result sees Table 1.
Table 1
| Performance | |
| A1 | Black box A1 completes 400 thermal shock cyclic tests, still can pass through air tightness test. |
| A2 | Black box A2 completes 400 thermal shock cyclic tests, still can pass through air tightness test. |
| A3 | Black box A3 completes 400 thermal shock cyclic tests, still can pass through air tightness test. |
| A4 | Black box A4 completes 400 thermal shock cyclic tests, still can pass through air tightness test. |
| D1 | Black box D1 fails to pass through air tightness test after completing 200 thermal shock cyclic tests. |
| D2 | Black box D2 fails to pass through air tightness test after completing 200 thermal shock cyclic tests. |
As can be seen from Table 1, the black box A1-4 that embodiments of the invention 1-4 makes still can pass through air tightness test after through 400 thermal shock cyclic tests, although and black box D3, D4 that Comparative Examples 2 is made fail to pass through air tightness test after through 200 thermal shock cyclic tests, the connection of black box that proves absolutely embodiments of the invention 1-4 made is reliable, good sealing effect.
Those skilled in the art easily know; the above is only preferred embodiment of the present invention; not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.Protection scope of the present invention is determined by claims.
Claims (10)
1. the black box of a battery, it is characterized in that, the black box of described battery comprises: ceramic ring, becket and stem stem, described ceramic ring is formed with endoporus, described becket is connected in outside described ceramic ring, described stem stem is connected in the endoporus of described ceramic ring, and described stem stem is the stem stem of titanium or titanium alloy, is provided with titanium parent metal layer between the stem stem of described titanium or titanium alloy and described ceramic ring.
2. the black box of battery according to claim 1, is characterized in that, described titanium alloy is selected from a kind of in titanium-aluminium alloy, titanium maxter alloy, titanium palldium alloy, ferro-titanium, Ti-Ni alloy.
3. the black box of battery according to claim 2, is characterized in that, described titanium parent metal comprises Ti, and comprise one or more in Zr, Ni, Cu.
4. the black box of battery according to claim 1, is characterized in that, described ceramic ring is a kind of in the compound ceramic ring of aluminium oxide ceramics ring, zirconia ceramics ring, alumina zirconia.
5. the black box of battery according to claim 1, is characterized in that, described becket is the aluminum or aluminum alloy ring.
6. the black box of battery according to claim 1 or 5, is characterized in that, also be provided with aluminium base solder layer between described becket and described ceramic ring, described aluminium base scolder comprises Al, and comprises one or both in Si, Mg.
7. the manufacture method as the black box of the described battery of claim 1-6 any one, is characterized in that, comprises the steps:
Step 1: the stem stem of titanium or titanium alloy is connected in the endoporus of ceramic ring;
Step 2: becket is connected in the outside of ceramic ring, obtains the black box of described battery.
8. manufacture method according to claim 7, is characterized in that, in step 1, the stem stem of titanium or titanium alloy is installed in the endoporus of ceramic ring, then adopts welding procedure that the stem stem of described titanium or the titanium alloy inner hole wall with ceramic ring is welded mutually; The scolder that described welding procedure adopts is the titanium parent metal, and the condition of welding procedure: under vacuum atmosphere, welding temperature is 830-900 ℃, and be 3-15 minute weld time.
9. manufacture method according to claim 7, is characterized in that, in step 2, described becket adopts soldering processes to be connected in the outside of ceramic ring; The scolder that described soldering processes adopt is aluminium base scolder, and described aluminium base scolder comprises Al, and comprises one or both in Si, Mg; The condition of soldering processes: brazing temperature is 570-660 ℃, and the holding time is 3-15 minute, and atmosphere is vacuum or inert gas atmosphere.
10. lithium ion battery, comprise: the housing of at least one end opening, be sealed in the black box of the openend of described housing, form seal cavity between described housing and black box, contain pole piece and electrolyte in described seal cavity, it is characterized in that, described black box adopts the black box as the described battery of claim 1-6 any one, wherein, described becket is connected with housing, and the stem stem of described titanium or titanium alloy is connected with described pole piece.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110379551XA CN103137917A (en) | 2011-11-25 | 2011-11-25 | Battery sealing assembly and production method thereof, and lithium ion battery |
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| CN201110379551XA CN103137917A (en) | 2011-11-25 | 2011-11-25 | Battery sealing assembly and production method thereof, and lithium ion battery |
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| CN201110379551XA Pending CN103137917A (en) | 2011-11-25 | 2011-11-25 | Battery sealing assembly and production method thereof, and lithium ion battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346274A (en) * | 2013-07-04 | 2013-10-09 | 深圳市科达利实业股份有限公司 | Power battery electrode sealing device and manufacturing method thereof |
| CN105576161A (en) * | 2016-02-03 | 2016-05-11 | 深圳市三讯电子有限公司 | Electrode terminal, power battery cover plate assembly and power battery |
| CN110071233A (en) * | 2019-04-10 | 2019-07-30 | 常州微宙电子科技有限公司 | Casing assembly and lithium ion battery for lithium ion battery |
| CN111446215A (en) * | 2020-05-11 | 2020-07-24 | 苏州融睿电子科技有限公司 | Packaging structure and method of packaging device and packaging device |
| US20210050579A1 (en) * | 2018-03-20 | 2021-02-18 | Indian Space Research Organization | Hermetically sealed lithium ion cells and a method for their manufacture |
| CN115360463A (en) * | 2022-08-05 | 2022-11-18 | 新化柏盛陶瓷科技有限公司 | Ceramic sealer for lithium battery and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346274A (en) * | 2013-07-04 | 2013-10-09 | 深圳市科达利实业股份有限公司 | Power battery electrode sealing device and manufacturing method thereof |
| CN103346274B (en) * | 2013-07-04 | 2016-01-27 | 深圳市科达利实业股份有限公司 | Power battery electrode sealing device and manufacture method thereof |
| CN105576161A (en) * | 2016-02-03 | 2016-05-11 | 深圳市三讯电子有限公司 | Electrode terminal, power battery cover plate assembly and power battery |
| US20210050579A1 (en) * | 2018-03-20 | 2021-02-18 | Indian Space Research Organization | Hermetically sealed lithium ion cells and a method for their manufacture |
| CN110071233A (en) * | 2019-04-10 | 2019-07-30 | 常州微宙电子科技有限公司 | Casing assembly and lithium ion battery for lithium ion battery |
| CN111446215A (en) * | 2020-05-11 | 2020-07-24 | 苏州融睿电子科技有限公司 | Packaging structure and method of packaging device and packaging device |
| CN115360463A (en) * | 2022-08-05 | 2022-11-18 | 新化柏盛陶瓷科技有限公司 | Ceramic sealer for lithium battery and preparation method thereof |
| CN115360463B (en) * | 2022-08-05 | 2024-04-16 | 新化柏盛陶瓷科技有限公司 | Ceramic sealer for lithium battery and preparation method thereof |
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Application publication date: 20130605 |