CN105731803A - Copper sealing glass powder, preparation method and application thereof, and electrodes of battery - Google Patents
Copper sealing glass powder, preparation method and application thereof, and electrodes of battery Download PDFInfo
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- CN105731803A CN105731803A CN201610109060.6A CN201610109060A CN105731803A CN 105731803 A CN105731803 A CN 105731803A CN 201610109060 A CN201610109060 A CN 201610109060A CN 105731803 A CN105731803 A CN 105731803A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/46—Bases; Cases
- H01R13/52—Dustproof, splashproof, drip-proof, waterproof, or flameproof cases
- H01R13/521—Sealing between contact members and housing, e.g. sealing insert
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/46—Bases; Cases
- H01R13/52—Dustproof, splashproof, drip-proof, waterproof, or flameproof cases
- H01R13/5216—Dustproof, splashproof, drip-proof, waterproof, or flameproof cases characterised by the sealing material, e.g. gels or resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/58—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation characterised by the form or material of the contacting members
- H01R4/62—Connections between conductors of different materials; Connections between or with aluminium or steel-core aluminium conductors
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Electrochemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses copper sealing glass powder, a preparation method and an application thereof, and electrodes of a battery, and relates to the field of glass sealing materials. The copper sealing glass powder solves the problems of poor matching property of thermal expansion coefficients, large sealing difficulty and instable sealing performance of the copper sealing glass powder and copper alloy materials. Raw materials of the copper sealing glass powder disclosed by the invention comprise components as follows in percentage by mass: 55%-75% of Bi2O3, 5%-15% of B2O3, 5%-20% of ZnO, 0.1%-20% of BaO, 0.1%-5% of SiO2, 0.1%-5% of Sb2O3, 0.1%-3% of Fe2O3 and 0.1%-5% of Li2O. The copper sealing glass powder has the advantages that the comprehensive performance is good, and particularly, the sealing temperature is relatively low while the thermal expansion coefficient of the copper sealing glass powder and the thermal expansion coefficient of the copper alloy materials are matched.
Description
Technical field
The present invention relates to sealing glass material field, particularly relate to a kind of copper sealing glass powder and preparation method and application and battery
Electrode.
Background technology
Sealing glass material is widely used in electrovacuum and microelectric technique, laser and infrared technique, high-energy physics, the energy, space
The various fields such as cosmos, automobile, it is achieved that the mutual sealing-in between glass, pottery, metal, quasiconductor.Sealing glass material needs tool
There is good thermostability need to have relatively low fusion temperature with chemical stability and higher mechanical strength, especially low temperature sealing glass
With sealing temperature.
Sealing glass material is when electronic devices and components sealing-in, and the thermal coefficient of expansion of seal glass need to be with the material of electronic devices and components
Thermal coefficient of expansion matches, when being Cu alloy material particularly with the housing of electric connector and contact, for sealing-in electric connector
The seal, sealing materials of housing and contact meet sealing temperature low with stable performance while, the thermal coefficient of expansion of this seal, sealing materials with
The thermal coefficient of expansion of copper alloy need to preferably mate.Such as, currently used high capacity cell is high because of its energy density, battery electricity
Pole is subjected to larger current, higher heat and corrosion resistant test, and the material such as traditional kovar alloy and rustless steel is as electrode
Material has been extremely difficult to above-mentioned requirements；Therefore, research worker has selected copper alloy as the material of battery electrode, Cu alloy material
Electric current transmission speed can be improved as battery electrode, reduce resistance loss and meet the growth requirement of above-mentioned high capacity cell.By copper
Alloyapplication, in battery electrode material, needs the housing of battery electrode reasonable in design and the structure of stem stem, more should be taken into account for
The coefficient of expansion of the glass material of sealing-in housing and stem stem must match with the thermal coefficient of expansion of copper alloy electrode material, copper alloy
Having higher thermal coefficient of expansion, it is 170 × 10 under the temperature conditions of 25 DEG C-300 DEG C-7-185×10-7/ DEG C, it is desirable to
Relatively low for glass material stable performance, good seal performance and the sealing temperature of sealing-in copper alloy electrode.
Currently used high expansion coefficient lead-free low-temperature seal glass mostly is phosphate glass, needs to produce under reducing atmosphere and seal
Connect, be unfavorable for commercial application, and glass physical and chemical performance extremely unstable, have a strong impact on the electrical insulation capability of sealing-in product, machinery
Performance and air-tightness etc..Prior art discloses the high expansion coefficient copper sealing glass powder of a kind of phosphoric acid salt, this copper seal glass
The sealing temperature of powder is 600 DEG C-780 DEG C, and the proportion of glass is 2-3.5, and the thermal coefficient of expansion of glass is 160 × 10-7-195
×10-7/ DEG C (25 DEG C-300 DEG C), and copper expansion coefficient similar, but P in the component of this copper seal powdered glass2O5Percent mass
Ratio up to 45%-65%, the more phosphorus of content can cause glass properties extremely unstable, and reliability is relatively low；Therefore, above-mentioned copper sealing-in
Glass dust is not suitable for the sealing-in of copper alloy electronic devices and components.It is SiO that prior art also discloses a kind of key component2、BaO
And Al2O3Copper sealing glass powder, the sealing temperature of this glass is 850 DEG C-890 DEG C, and the proportion of glass is 2.86-3.06, heat
The coefficient of expansion is 88 × 10-7-92×10-7/ DEG C (25 DEG C-400 DEG C), the sealing temperature of this glass dust is higher, increases sealing-in
Difficulty, thermal coefficient of expansion is on the low side, poor with the coefficient of expansion matching of copper；Therefore, above-mentioned copper sealing glass powder is not suitable for yet
The sealing-in of copper alloy electronic devices and components.Above two copper sealing glass powder is particularly unsuitable for the sealing-in of copper alloy electric connector, more
It is not suitable for the sealing-in of the copper core aluminum hull electrode of high capacity cell.
Summary of the invention
In view of this, embodiments provide a kind of copper sealing glass powder and preparation method and application and the electrode of battery,
Main purpose is that solution copper sealing glass powder is poor with the matched coefficients of thermal expansion of copper alloy, and sealing-in difficulty is big and sealing property is unstable
Fixed problem.
For reaching above-mentioned purpose, invention broadly provides following technical scheme:
On the one hand, the invention provides a kind of copper sealing glass powder, its raw material is made up of the component of following weight/mass percentage composition:
As preferably, the raw material of described copper sealing glass powder is made up of the component of following weight/mass percentage composition:
As preferably, described B2O3Mass ratio 0.5-1.2:1 with ZnO.
As preferably, described copper sealing glass powder thermal coefficient of expansion under the conditions of 20 DEG C-300 DEG C is 105 × 10-7-130×
10-71/℃。
As preferably, the softening temperature of described copper sealing glass powder is 330 DEG C-470 DEG C；The transformation temperature of described copper sealing glass powder
Degree is 302 DEG C-410 DEG C.
As preferably, the sealing temperature of described copper sealing glass powder is 480 DEG C-600 DEG C；The proportion of described copper sealing glass powder is
3.8-4.4。
On the other hand, the invention provides the preparation method of above-mentioned copper sealing glass powder, the method includes: prepare by composition of raw materials
Glass mixture, is fused into vitreous humour by described glass mixture, is cooled down by described vitreous humour and makes sheet glass, by described glass
Glass sheet makes the former powder of glass, and the former powder of described glass obtains copper sealing glass powder after crossing the screen cloth of 120 mesh-200 mesh.
As preferably, the corundum crucible being contained with described glass mixture is put into the Muffle furnace that temperature is 200 DEG C-300 DEG C pre-
After hot 20min-40min, place into and obtain described vitreous humour after the electric furnace that furnace temperature is 900 DEG C-1100 DEG C is incubated 1.5-3h；
Cool down in described vitreous humour is poured into tablet machine and tabletting obtains described sheet glass；Described sheet glass is put into Ceramic Balls grinding jar ball
Mill 3h-5h obtains described glass dust, and described glass dust obtains described copper sealing glass powder after crossing 120 mesh-150 eye mesh screens.
Another further aspect, the invention provides the application in the sealing-in of electric connector of the above-mentioned copper sealing glass powder.
As preferably, described electric connector is the copper core aluminum hull electrode of battery.
Another aspect, the invention provides the electrode of a kind of battery, including Al-alloy casing, copper alloy stem stem and for sealing-in shell
Body and the seal, sealing materials of stem stem, described seal, sealing materials is above-mentioned copper sealing glass powder.
Compared with prior art, the invention has the beneficial effects as follows:
The matched coefficients of thermal expansion that the present invention is directed to copper sealing glass material and copper alloy electronic devices and components is poor, sealing temperature height and
The technical problem that sealing property is unstable, uses bismuthates system glass as copper sealing glass material, has specificity by selection
Can component and regulate each component mass content in bismuthate glass, enable each component mutually synergism, the copper obtained
The thermal coefficient of expansion of sealing glass powder more mate with the thermal coefficient of expansion of copper alloy while copper sealing glass powder for sealing-in copper
The sealing temperature of alloy electronic devices and components is relatively low, and reduces sealing-in difficulty and energy consumption；The chemistry of described copper sealing glass powder
The combination properties such as performance, gas tightness and mechanical strength are good, and Technological adaptability is good, it is easy to preparation processing, reduce and produce into
Originally, improve economic benefit and expand range.
Detailed description of the invention
By further illustrating the technological means and effect that the present invention taked by reaching predetermined goal of the invention, below preferably to implement
Example, to the foundation detailed description of the invention of the present patent application, technical scheme, feature and effect thereof, after describing in detail such as.Under state
Special characteristic, structure or feature in multiple embodiments in bright can be combined by any suitable form.
Embodiment 1
According to following component and component proportion weigh correspondence raw material:
Bi2O355%, B2O310%, ZnO 10%, BaO 10%, SiO25%, Sb2O35%, Fe2O33%, Li2O 2%；
The raw material of above-mentioned correspondence is followed successively by bismuth oxide, boric acid, zinc oxide, brium carbonate, silicon dioxide, ferrum oxide and Lithium hydrate
Raw material；
Glass mixture is obtained after being sufficiently mixed by above-mentioned raw materials and grind uniformly；Above-mentioned glass mixture is put into corundum crucible
In, then set temperature in being positioned over by corundum crucible as the Muffle furnace of 200 DEG C preheats 40min；Preheating will be contained with glass after terminating
The corundum crucible of glass compound is positioned in the electric furnace that furnace temperature temperature is 900 DEG C insulation fusing 3.0h, and insulation is clarified after terminating
Pale-yellow galss liquid；Being poured into by vitreous humour in the tablet machine with water cooling function, it is same that vitreous humour is water cooled solidification in tablet machine
Time be compressed to sheet glass；The former powder of glass is obtained after above-mentioned sheet glass is put into Ceramic Balls grinding jar ball milling 5h；By above-mentioned glass
Former powder obtains copper sealing glass powder after crossing 120 eye mesh screens；
The employing dilatometer above-mentioned copper sealing glass powder of measurement is 105 × 10 at the thermal coefficient of expansion of 20 DEG C-300 DEG C-7/ DEG C, by height
It is 585 DEG C that temperature microscope obtains the sealing temperature of this copper sealing glass powder.
Embodiment 2
According to following component and component proportion weigh correspondence raw material:
Bi2O360%, B2O315%, ZnO 15%, BaO 3.5%, SiO20.5%, Sb2O32%, Fe2O32%, Li2O
2%；The raw material of above-mentioned correspondence is followed successively by bismuth oxide, boric acid, zinc oxide, brium carbonate, silicon dioxide, ferrum oxide and hydrogen-oxygen
Change lithium raw material；
Glass mixture is obtained after being sufficiently mixed by above-mentioned raw materials and grind uniformly；Above-mentioned glass mixture is put into corundum crucible
In, then set temperature in being positioned over by corundum crucible as the Muffle furnace of 250 DEG C preheats 25min；Preheating will be contained with glass after terminating
The corundum crucible of glass compound is positioned in the electric furnace that furnace temperature temperature is 950 DEG C insulation fusing 2.0h, and insulation is clarified after terminating
Pale-yellow galss liquid；Being poured into by vitreous humour in the tablet machine with water cooling function, it is same that vitreous humour is water cooled solidification in tablet machine
Time be compressed to sheet glass；The former powder of glass is obtained after above-mentioned sheet glass is put into Ceramic Balls grinding jar ball milling 3.5h；By above-mentioned glass
The former powder of glass obtains copper sealing glass powder after crossing 125 eye mesh screens；
The employing dilatometer above-mentioned copper sealing glass powder of measurement is 108 × 10 at the thermal coefficient of expansion of 20 DEG C-300 DEG C-7/ DEG C, by height
It is 567 DEG C that temperature microscope obtains the sealing temperature of this copper sealing glass powder.
Embodiment 3
According to following component and component proportion weigh correspondence raw material:
Bi2O365%, B2O312%, ZnO 9%, BaO 8%, SiO22%, Sb2O32%, Fe2O31%, Li2O 1%；
The raw material of above-mentioned correspondence is followed successively by bismuth oxide, boric acid, zinc oxide, brium carbonate, silicon dioxide, ferrum oxide and Lithium hydrate
Raw material；
Glass mixture is obtained after being sufficiently mixed by above-mentioned raw materials and grind uniformly；Above-mentioned glass mixture is put into corundum crucible
In, then set temperature in being positioned over by corundum crucible as the Muffle furnace of 280 DEG C preheats 30min；Preheating will be contained with glass after terminating
The corundum crucible of glass compound is positioned in the electric furnace that furnace temperature temperature is 1000 DEG C insulation fusing 2.5h, and insulation obtains clear after terminating
Clear pale-yellow galss liquid；Being poured into by vitreous humour in the tablet machine with water cooling function, vitreous humour is water cooled solidification in tablet machine
It is compressed to sheet glass simultaneously；The former powder of glass is obtained after above-mentioned sheet glass is put into Ceramic Balls grinding jar ball milling 4h；By above-mentioned glass
The former powder of glass obtains copper sealing glass powder after crossing 130 eye mesh screens；
The employing dilatometer above-mentioned copper sealing glass powder of measurement is 112 × 10 at the thermal coefficient of expansion of 20 DEG C-300 DEG C-7/ DEG C, by height
It is 547 DEG C that temperature microscope obtains the sealing temperature of this copper sealing glass powder.
Embodiment 4
According to following component and component proportion weigh correspondence raw material:
Bi2O371%, B2O37%, ZnO 10%, BaO 5%, SiO23%, Sb2O32%, Fe2O31%, Li2O 1%；
The raw material of above-mentioned correspondence is followed successively by bismuth oxide, boric acid, zinc oxide, brium carbonate, silicon dioxide, ferrum oxide and Lithium hydrate
Raw material；
Glass mixture is obtained after being sufficiently mixed by above-mentioned raw materials and grind uniformly；Above-mentioned glass mixture is put into corundum crucible
In, then set temperature in being positioned over by corundum crucible as the Muffle furnace of 290 DEG C preheats 35min；Preheating will be contained with glass after terminating
The corundum crucible of glass compound is positioned in the electric furnace that furnace temperature temperature is 1050 DEG C insulation fusing 2.5h, and insulation obtains clear after terminating
Clear pale-yellow galss liquid；Being poured into by vitreous humour in the tablet machine with water cooling function, vitreous humour is water cooled solidification in tablet machine
It is compressed to sheet glass simultaneously；The former powder of glass is obtained after above-mentioned sheet glass is put into Ceramic Balls grinding jar ball milling 4.5h；By above-mentioned
The former powder of glass obtains copper sealing glass powder after crossing 135 eye mesh screens；
The employing dilatometer above-mentioned copper sealing glass powder of measurement is 120 × 10 at the thermal coefficient of expansion of 20 DEG C-300 DEG C-7/ DEG C, by height
It is 510 DEG C that temperature microscope obtains the sealing temperature of this copper sealing glass powder.
Embodiment 5
According to following component and component proportion weigh correspondence raw material:
Bi2O373%, B2O36%, ZnO 11%, BaO 5%, SiO22%, Sb2O31%, Fe2O31%, Li2O 1%；
The raw material of above-mentioned correspondence is followed successively by bismuth oxide, boric acid, zinc oxide, brium carbonate, silicon dioxide, ferrum oxide and Lithium hydrate
Raw material；
Glass mixture is obtained after being sufficiently mixed by above-mentioned raw materials and grind uniformly；Above-mentioned glass mixture is put into corundum crucible
In, then set temperature in being positioned over by corundum crucible as the Muffle furnace of 295 DEG C preheats 38min；Preheating will be contained with glass after terminating
The corundum crucible of glass compound is positioned in the electric furnace that furnace temperature temperature is 1050 DEG C insulation fusing 3h, and insulation is clarified after terminating
Pale-yellow galss liquid；Being poured into by vitreous humour in the tablet machine with water cooling function, it is same that vitreous humour is water cooled solidification in tablet machine
Time be compressed to sheet glass；The former powder of glass is obtained after above-mentioned sheet glass is put into Ceramic Balls grinding jar ball milling 5h；By above-mentioned glass
Former powder obtains copper sealing glass powder after crossing 140 eye mesh screens；
The employing dilatometer above-mentioned copper sealing glass powder of measurement is 125 × 10 at the thermal coefficient of expansion of 20 DEG C-300 DEG C-7/ DEG C, by height
It is 501 DEG C that temperature microscope obtains the sealing temperature of this copper sealing glass powder.
Embodiment 6
According to following component and component proportion weigh correspondence raw material:
Bi2O375%, B2O35%, ZnO 8%, BaO 7%, SiO22%, Sb2O31%, Fe2O31%, Li2O 1%；
The raw material of above-mentioned correspondence is followed successively by bismuth oxide, boric acid, zinc oxide, brium carbonate, silicon dioxide, ferrum oxide and Lithium hydrate
Raw material；
Glass mixture is obtained after being sufficiently mixed by above-mentioned raw materials and grind uniformly；Above-mentioned glass mixture is put into corundum crucible
In, then set temperature in being positioned over by corundum crucible as the Muffle furnace of 300 DEG C preheats 20min；Preheating will be contained with glass after terminating
The corundum crucible of glass compound is positioned in the electric furnace that furnace temperature temperature is 1100 DEG C insulation fusing 1.5h, and insulation obtains clear after terminating
Clear pale-yellow galss liquid；Being poured into by vitreous humour in the tablet machine with water cooling function, vitreous humour is water cooled solidification in tablet machine
It is compressed to sheet glass simultaneously；The former powder of glass is obtained after above-mentioned sheet glass is put into Ceramic Balls grinding jar ball milling 5h；By above-mentioned glass
The former powder of glass obtains copper sealing glass powder after crossing 150 eye mesh screens；
The employing dilatometer above-mentioned copper sealing glass powder of measurement is 129 × 10 at the thermal coefficient of expansion of 20 DEG C-300 DEG C-7/ DEG C, by height
It is 492 DEG C that temperature microscope obtains the sealing temperature of this copper sealing glass powder.
Embodiment 7
The present embodiment is with the difference of embodiment 6, is according to following component when preparing the copper sealing glass powder of the present embodiment
And component proportion weigh correspondence raw material:
Bi2O372%, B2O37%, ZnO 10%, BaO 5%, SiO22%, Sb2O31%, Fe2O31%, Li2O 1%；
The raw material of above-mentioned correspondence is followed successively by bismuth oxide, boric acid, zinc oxide, brium carbonate, silicon dioxide, ferrum oxide and Lithium hydrate
Raw material；Wherein, B2O3It is 0.7:1.0 with the mass ratio of ZnO；
Glass mixture is obtained after being sufficiently mixed by above-mentioned raw materials and grind uniformly；Above-mentioned glass mixture is put into corundum crucible
In, then set temperature in being positioned over by corundum crucible as the Muffle furnace of 300 DEG C preheats 20min；Preheating will be contained with glass after terminating
The corundum crucible of glass compound is positioned in the electric furnace that furnace temperature temperature is 1100 DEG C insulation fusing 1.5h, and insulation obtains clear after terminating
Clear pale-yellow galss liquid；Being poured into by vitreous humour in the tablet machine with water cooling function, vitreous humour is water cooled solidification in tablet machine
It is compressed to sheet glass simultaneously；The former powder of glass is obtained after above-mentioned sheet glass is put into Ceramic Balls grinding jar ball milling 5h；By above-mentioned glass
The former powder of glass obtains copper sealing glass powder after crossing 150 eye mesh screens；
The employing dilatometer above-mentioned copper sealing glass powder of measurement is 125 × 10 at the thermal coefficient of expansion of 20 DEG C-300 DEG C-7/ DEG C, by height
It is 498 DEG C that temperature microscope obtains the sealing temperature of this copper sealing glass powder.
By detecting the coefficient of expansion and the sealing temperature of copper sealing glass powder prepared by embodiment 1-6, it can be seen that the embodiment of the present invention
The coefficient of expansion of six kinds of copper sealing glass powders of preparation is in 105 × 10-7-129×10-7Between, copper alloy is at 25 DEG C-300 DEG C
Under temperature conditions, its thermal coefficient of expansion is 170 × 10-7-185×10-7/℃；It follows that use embodiment of the present invention 1-6
The coefficient of expansion of copper seal glass of preparation more mates with the thermal coefficient of expansion of copper alloy；Copper sealing-in glass prepared by embodiment 1-6
Glass powder sealing temperature when sealing-in is in 492 DEG C-585 DEG C, and sealing temperature is relatively low；The copper sealing-in of the embodiment of the present invention
Glass dust is meeting while thermal coefficient of expansion more mates with the thermal coefficient of expansion of copper alloy, also meets for sealing-in copper alloy material
The requirement that sealing temperature during material is relatively low.
In the embodiment of the present invention, copper seal glass belongs to bismuthate glass system, and the most each component role is as follows:
Bi2O3The effect of Network former is played in this glass；Work as Bi2O3> 75% time, the coefficient of expansion of glass is relatively big, glass machinery
Intensity reduces, fragility increases, and is not easy to the sealing-in of Cu alloy material, and meanwhile, cost has bigger rising；Work as Bi2O3< when 55,
The coefficient of expansion of glass reduces, and sealing temperature is obviously improved；According to Bi2O3Comprehensive function in copper sealing glass powder, its glass
Middle Bi2O3Mass percent be 55%-75%；As Bi in glass2O3Mass percent be 60%-70%, copper sealing glass powder
Sealing temperature and chemical stability are more preferably；
B2O3It is to form glass oxide, is also the composition constituting glass skeleton, be again simultaneously a kind of to reduce glass smelting viscosity
Cosolvent；Work as B2O3> 15% time, improve glass softening point, improve the crystallize ability of glass simultaneously；Work as B2O3< when 5%, glass
The coefficient of expansion of glass, heat stability and chemical stability reduce；According to B2O3Comprehensive function in copper sealing glass powder, its glass
B in glass2O3Mass percent be 5%-15%；As B in glass2O3Mass percent be 7%-12%, copper sealing glass powder is more
Stable, it is difficult to crystallize；
ZnO is network modifying oxide；As ZnO > 20% time, glass is prone to crystallize when sealing-in；When ZnO < when 5%, reduces glass
The effect of the coefficient of expansion of glass, the chemical stability improving glass and heat stability is inconspicuous；According to ZnO at copper sealing glass powder
In comprehensive function, in its glass, the mass percent of ZnO is 5%-20%；When in glass, the mass percent of ZnO is 10%-15%,
Copper sealing glass powder is more stable, is difficult to crystallize；
BaO is network modifying oxide, regulates glass expansion coefficient, accelerates the fusing of glass, increases resistivity and Jie of glass
Electric constant；Work as BaO > 20%, make the clarification difficulty of glass, meanwhile, increase the coefficient of expansion of glass；When BaO < when 5%, glass
The chemical stability of glass reduces；According to BaO comprehensive function in copper sealing glass powder, the mass percent of BaO in its glass
For 5%-20%；Further preferably 5%-15%, resultant effect is more preferable；
SiO2Chemical durability of glass, heat stability and mechanical performance is mainly regulated in this glass；Work as SiO2> 5 time, improve
The sealing temperature of glass；Work as SiO2< when 0.1, reduce the chemical stability of glass, heat stability and mechanical performance；According to SiO2
Comprehensive function in copper sealing glass powder, SiO in its glass2Mass percent be 0.1%-5%；As SiO in glass2Matter
Amount percentage ratio is 1%-3%, and resultant effect is more preferable；
Sb2O3Sealing temperature is mainly reduced in this glass；Work as Sb2O3> 5 time, the easy crystallize of glass, the sealing temperature liter of glass
High；Work as Sb2O3< when 0.1, faint on sealing temperature impact；According to Sb2O3Comprehensive function in copper sealing glass powder, its glass
Sb in glass2O3Mass percent be 0.1%-5%；As Sb in glass2O3Mass percent be 1%-3%, sealing temperature reduce,
And it is difficult to crystallize；
Fe2O3Sealing temperature is mainly reduced in this glass；Work as Fe2O3> 3 time, improve glass sealing temperature raise；When
Fe2O3< when 0.1, faint on sealing temperature impact；According to Fe2O3Comprehensive function in copper sealing glass powder, Fe in its glass2O3
Mass percent be 0.1%-3%；As Fe in glass2O3Mass percent be 1%-2%, sealing temperature reduce, and be difficult to analysis
Brilliant；
Li2O mainly reduces sealing temperature in this glass, regulates the coefficient of expansion；Work as Li2During O > 5%, devitrification of glass tendency and
The coefficient of expansion increases；Work as Li2O is < when 0.1%, inconspicuous with the effect of the sealing temperature reducing glass to the fluxing action of glass；
According to Li2O comprehensive function in copper sealing glass powder, Li in its glass2The weight/mass percentage composition of O is 0.1%-5%；Work as glass
Middle Fe2O3Mass percent be 1%-2%, resultant effect is more preferable.
B in the raw material of the copper sealing glass powder of the present invention2O3With the mass ratio 0.5-1.2:1 of ZnO, devitrification of glass is inclined by this ratio
To relatively big with sealing temperature impact, when using the ratio of 0.5-1.2:1 of the present invention, the performance ratio of the copper sealing glass powder of preparation
More stable；Work as B2O3When being more than 1.2:1 with the mass ratio of ZnO, improve the sealing temperature of glass；Work as B2O3Matter with ZnO
When amount ratio is less than 0.5:1, glass easily crystallize, affect glass properties；Therefore, B is limited2O3With ZnO two oxides quality
Proportion be 0.5-1.2:1, be the key of the copper sealing glass powder founding out stable performance.
The softening temperature that the present invention uses Germany's NETZSCH company DIOL402 type dilatometer to measure copper sealing glass powder is 330 DEG C
-470 DEG C, transition temperature is 302 DEG C-410 DEG C；It is 3.8-4.4 that suspension method measures proportion.
The sealing temperature of the copper sealing glass powder of the present invention is relatively low, protects by the architectural characteristic of seal, sealing materials, reduces envelope
Connect difficulty and energy consumption；Being tested by helium mass spectrometer leak detector, the gas tightness of the copper sealing glass powder of the present invention is excellent；Further through
10951 type dielectric strength tester tests, the electrical insulation capability of the copper sealing glass powder of the present invention is good, breakdown strength is higher；According to
Standard SJ/T 11035-96 record the copper sealing glass powder of the present invention chemical property excellent.
In the component of the copper sealing glass powder of the present invention the most leaded, meet WEEE, RoHS instruction environmental requirement.
The copper sealing glass powder Technological adaptability of the present invention is good, it is easy to preparation processing, reduces production cost and increases economic efficiency.
The preparation method of the copper sealing glass powder of embodiments of the invention 1-7 is simple to operation, be not required in reducing atmosphere preparation and
Sealing-in, beneficially large-scale production, use roll-in method cooling and solidifying vitreous humour to make ball grinds in hgher efficiency, and ensure that preparation
The stable performance of copper sealing glass powder, it is ensured that electrical insulation capability, mechanical performance and the air-tightness of sealing-in product such as electric connector
Well.
The copper sealing glass powder of the present invention is applicable to the sealing-in of copper alloy electronic devices and components, is particularly suited for copper alloy electric connector
Sealing-in, such as by housing and stem stem, its good sealing effect, the electric property of the copper sealing glass powder sealing-in electric connector of the present invention
Preferably, mechanical strength is high and electrical insulating property is good etc..
The copper sealing glass powder of the present invention is more suitable for the sealing-in of the copper core aluminum hull electrode of high capacity cell, because the shell of battery electrode
Body is aluminium material, and the melt temperature of aluminum is at 660 DEG C, and the core column material of the electrode of battery is copper alloy, therefore the copper core aluminum of battery
Shell electrode is high to the performance requirement of its seal, sealing materials, it is desirable to the thermal coefficient of expansion of its seal, sealing materials will be with the Cu alloy material of stem stem
Thermal coefficient of expansion match, the most also require the melted temperature of the aluminum alloy materials of the sealing temperature housing to be less than of its seal, sealing materials
Degree, existing sealing glass material is all relatively inaccessible to above-mentioned requirements；And the thermal coefficient of expansion of the copper sealing glass powder of the present invention and copper
Thermal coefficient of expansion match, sealing temperature is relatively low, less than the melt temperature of aluminum, for the envelope of the copper core aluminum hull electrode of battery
Connect effect the best.
The combination property of the copper sealing glass powder of the present invention is good, can be used for copper alloy, aluminium alloy and stainless steel sealed field, expands
Big range.
The not most part of the embodiment of the present invention, those skilled in the art can be known from prior art.
The detailed description of the invention being only the present invention disclosed above, but protection scope of the present invention is not limited thereto, any ripe
Know those skilled in the art in the technical scope that the invention discloses, change can be readily occurred in or replace, all should contain
Within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with above-mentioned scope of the claims.
Claims (11)
1. a copper sealing glass powder, it is characterised in that its raw material is made up of the component of following weight/mass percentage composition:
A kind of copper sealing glass powder the most according to claim 1, it is characterised in that its raw material is by following weight/mass percentage composition
Component composition:
A kind of copper sealing glass powder the most according to claim 1, it is characterised in that described B2O3With the mass ratio of ZnO it is
0.5-1.2:1。
A kind of copper sealing glass powder the most according to claim 1, it is characterised in that the thermal expansion of described copper sealing glass powder
Coefficient is 105 × 10-7-130×10-71/℃。
A kind of copper sealing glass powder the most according to claim 1, it is characterised in that the softening temperature of described copper sealing glass powder
Degree is 330 DEG C-470 DEG C；The transition temperature of described copper sealing glass powder is 302 DEG C-410 DEG C.
A kind of copper sealing glass powder the most according to claim 1, it is characterised in that the sealing-in temperature of described copper sealing glass powder
Degree is 480 DEG C-600 DEG C；The proportion of described copper sealing glass powder is 3.8-4.4.
7. the preparation method of a kind of copper sealing glass powder described in any one of claim 1-6, it is characterised in that by composition of raw materials
Prepare glass mixture, described glass mixture is fused into vitreous humour, described vitreous humour is cooled down and makes sheet glass, by institute
Stating sheet glass and make the former powder of glass, the former powder of described glass obtains copper sealing glass powder after crossing the screen cloth of 120 mesh-200 mesh.
The preparation method of a kind of copper sealing glass powder the most according to claim 7, it is characterised in that described glass will be contained with
After the Muffle furnace preheating 20min-40min that temperature is 200 DEG C-300 DEG C put into by the corundum crucible of glass compound, place into furnace temperature
It is that the electric furnace of 900 DEG C-1100 DEG C obtains described vitreous humour after insulation 1.5-3h；Cool down in described vitreous humour is poured into tablet machine
And tabletting obtains described sheet glass；Described sheet glass is put into Ceramic Balls grinding jar ball milling 3h-5h and obtains described glass dust, described
Glass dust obtains described copper sealing glass powder after crossing 120 mesh-150 eye mesh screens.
9. the application of a copper sealing glass powder, it is characterised in that described copper sealing glass powder is for the sealing-in of electric connector.
The application of a kind of copper sealing glass powder the most according to claim 9, it is characterised in that described electric connector is electricity
The copper core aluminum hull electrode in pond.
The electrode of 11. 1 kinds of batteries, including Al-alloy casing, copper alloy stem stem and for sealing-in housing and the seal, sealing materials of stem stem,
It is characterized in that, described seal, sealing materials is the copper sealing glass powder described in any one of claim 1-6.
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| CN201610109060.6A CN105731803A (en) | 2016-02-26 | 2016-02-26 | Copper sealing glass powder, preparation method and application thereof, and electrodes of battery |
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| CN201610109060.6A CN105731803A (en) | 2016-02-26 | 2016-02-26 | Copper sealing glass powder, preparation method and application thereof, and electrodes of battery |
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| CN109494415A (en) * | 2018-12-28 | 2019-03-19 | 西安赛尔电子材料科技有限公司 | A kind of glass sealing method of lithium ion battery cover board component T aluminium poles and Stainless Steel Shell |
| CN112897884A (en) * | 2021-02-22 | 2021-06-04 | 合肥邦诺科技有限公司 | Preformed low-temperature glass soldering lug and screen printing manufacturing method thereof |
| CN113121117A (en) * | 2020-01-10 | 2021-07-16 | 中国科学院上海硅酸盐研究所 | Glass powder suitable for OLED packaging and preparation method and application thereof |
| CN116833620A (en) * | 2023-08-29 | 2023-10-03 | 长春理工大学 | Bi-containing solder and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112897884A (en) * | 2021-02-22 | 2021-06-04 | 合肥邦诺科技有限公司 | Preformed low-temperature glass soldering lug and screen printing manufacturing method thereof |
| CN112897884B (en) * | 2021-02-22 | 2022-04-19 | 合肥邦诺科技有限公司 | Preformed low-temperature glass soldering lug and screen printing manufacturing method thereof |
| CN116833620A (en) * | 2023-08-29 | 2023-10-03 | 长春理工大学 | Bi-containing solder and preparation method and application thereof |
| CN116833620B (en) * | 2023-08-29 | 2023-12-01 | 长春理工大学 | Bi-containing solder and preparation method and application thereof |
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