CN209045627U - A kind of glass-sealed seal assembly of aluminum hull power battery electrode pole - Google Patents

A kind of glass-sealed seal assembly of aluminum hull power battery electrode pole Download PDF

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Publication number
CN209045627U
CN209045627U CN201821794411.2U CN201821794411U CN209045627U CN 209045627 U CN209045627 U CN 209045627U CN 201821794411 U CN201821794411 U CN 201821794411U CN 209045627 U CN209045627 U CN 209045627U
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China
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glass
cover board
electrode
battery cover
electrode stem
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缪锡根
申亮
潘华路
周小鹏
何纪生
缪波
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Shenzhen Zhongao new porcelain Technology Co.,Ltd.
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Australia Branch (shenzhen) New Material Co Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The utility model discloses a kind of glass-sealed seal assemblies of aluminum hull power battery electrode pole.The seal assembly includes electrode stem, electrodes base, battery cover board, seal glass;Seal glass includes lantern ring, inner coating and external coating;Battery cover board is equipped with through-hole corresponding with electrode stem;Electrode stem is set on electrodes base, and battery cover board passes through electrode stem and is located on electrodes base;Lantern ring is sheathed on electrode stem, and lantern ring is between electrode stem and battery cover board;Inner coating, external coating are coated on the internal diameter and outer diameter of lantern ring, and inner coating is close to the outer diameter setting of electrode stem, and external coating is close to the through-hole setting of battery cover board;The utility model can be melted by setting seal glass and washer, the coat of inner coating, external coating and washer in sealing electrode seal assembly, infiltrated aluminum battery cover board and electrode terminal, played the sealing effect with chemical bond interface cohesion.

Description

A kind of glass-sealed seal assembly of aluminum hull power battery electrode pole
Technical field
The utility model relates to a kind of glass-sealed seal assemblies of electrode terminal, belong to aluminum hull power battery technology neck A kind of domain, and in particular to glass-sealed seal assembly of aluminum hull power battery electrode pole.
Background technique
Battery refers to the device that chemical energy can be converted to electric energy for filling electrode, diaphragm and electrolyte solution, has just Pole, cathode point.The performance parameter of battery mainly has electromotive force, capacity, specific energy and resistance etc..Utilize the battery as energy Source, it is available that there is burning voltage, stabling current, long-time stable power supply and the electric current that very little is influenced by the external world.Battery knot Structure is simple, easy to carry, and charge and discharge are easy to operation, is not influenced by outside climatic and temperature, stable and reliable for performance, existing There is great role for the various aspects performance in social life.
Chargeable lithium ion battery, structure include battery core, accommodate the battery case of battery core and the battery of battery case one end Cover plate assembly.Battery core includes negative plate, positive plate, the diaphragm for preventing short circuit between positive/negative plate and electrolyte etc.. Battery core is fitted into the battery case or shell of stainless steel, plastic housing, aluminum metal case or flexible packaging film.Battery core and extraneous electricity Conducting is completed by the connection sheet on the tab and pole that connect with pole plate.The composition of battery cover board assembly includes fluid injection Mouth, explosion-proof valve, positive electrode through-hole and negative electrode through-hole, between the positive and negative electrode pole and through-hole and pole of through-hole Sealing material or sealing structure.
The why important sealing of aluminum hull power rectangular lithium ion battery is because of existing electrolyte (all solid state lithium ion Except battery) there is serious corrosivity.Specifically, the electrolyte of lithium ion battery generally contains hexafluoro phosphorus lithium (LiPF6) Organic matter mixed liquor mixes with electrolyte if the water or steam outside battery penetrate into battery, will form hydrofluoric acid (HF) Heavy corrosion battery component is caused short circuit even to cause an explosion accident by solution: if electrolyte leakage to battery surface it Outside, the moisture in extraneous water or air can equally react with electrolyte, badly damaged battery, to the safety of automobile and make Fatal adverse effect is caused with the service life.
The leakproof seal method of the electrode terminal of existing aluminum hull power lithium-ion battery mostly uses traditional plastics close Encapsulation technique, however people more and more clearly recognize, plastics sealing-in is easy to be corroded intolerant to temperature, aging, resisting temperature variability Can be poor, non-seismic dynamic, the service life is short, and interface causes to be easy leakage without chemical bonds;Another practical power electric Pond electrode process for sealing is metallized ceramic sealing-in, however ceramics and intermetallic welding are more difficult, and metallization material is not Corrosion-resistant to need to add protective coating, furthermore ceramics itself are frangible, cause welding process to generate since thermal expansion coefficient is larger remaining Thermal stress, the presence of these corrosion tendencies and interfacial thermal stress cause to damage the reliability of closure, stability and use the longevity Life, in addition there are the disadvantages of manufacturing process complexity.
Main problem existing for aluminum current-lead glass sealing-in is to find heat shock resistance and the resistance to mechanical punching of existing seal glass It hits performance and does not meet requirement.Existing many domestic utility model patents do not consider electrode terminal glass seal packs Mechanical firmness problem fails to illustrate specific sealing glass material and how to match the thermal expansion coefficient of each component, leads to reality Glass sealing feasibility on border is not good enough.
Utility model content
The purpose of the utility model is to overcome the defects of the prior art, provide a kind of aluminum hull power battery electrode pole glass The seal assembly of sealing-in does not meet the technology of requirement to solve heat shock resistance and the mechanical shock resistance of seal glass Problem.
To solve the above-mentioned problems, the utility model is achieved by technical solution below:
A kind of glass-sealed seal assembly of aluminum hull power battery electrode pole, including electrode stem, electrodes base, battery Cover board, seal glass;Electrode stem is set on the electrodes base, and the battery cover board passes through the electrode stem and is located at institute It states on electrodes base;The battery cover board is equipped with through-hole corresponding with the electrode stem;
The seal glass includes lantern ring, inner coating and external coating;
The lantern ring is sheathed on the electrode stem, and lantern ring be located at the electrode stem and the battery cover board it Between;The inner coating, the external coating are coated on the internal diameter and outer diameter of the lantern ring, and the inner coating is close to the electrode The outer diameter of stem is arranged, and the external coating is close to the through-hole setting of the battery cover board.
The glass-sealed seal assembly of aluminum hull power battery electrode pole of the utility model embodiment, further includes washer, The washer passes through the electrode stem and is located on the electrodes base, and is located under the inner coating, the battery cover board;Pad It encloses surface and coat is set.
The glass-sealed seal assembly of aluminum hull power battery electrode pole of the utility model embodiment, further includes convex annular Platform, the annular convex platform are set on the battery cover board, and are connect with the battery cover board integral type.
The glass-sealed seal assembly of aluminum hull power battery electrode pole of the utility model embodiment, further includes annulus Set, the annulus set are set on the battery cover board across the electrode stem, and the internal diameter of annulus set and the convex annular The outer diameter of platform is identical.
The glass-sealed seal assembly of aluminum hull power battery electrode pole of the utility model embodiment, further includes top layer, The top layer is set on the seal glass.
The glass-sealed seal assembly of aluminum hull power battery electrode pole of the utility model embodiment further includes sealing Ring, the sealing ring pass through the electrode stem and are set on the battery cover board, and the internal diameter of sealing ring and the through-hole Diameter is identical.
The glass-sealed seal assembly of aluminum hull power battery electrode pole of the utility model embodiment, further include washer and Annular convex platform, the washer passes through the electrode stem and is located on the electrodes base, and is located under the battery cover board;It is described Annular convex platform is set on the battery cover board, and is connect with the battery cover board integral type.
The beneficial effects of the utility model are:
1) by setting seal glass and washer, the coat of inner coating, external coating and washer is in sealing electrode sealing group It can be melted when part, infiltrate aluminum battery cover board and electrode terminal, play the sealing effect with chemical bond interface cohesion;Glass Seal interface has chemical bonds, has more air-tightness than plastics machinery pressing sealing technique, while glass is than the weatherability of plastics It is good;
2) the utility model using the second phase of aluminium alloy make the intensity, toughness of corrosion-resistant low temperature sealing glass, thermal conductivity and Thermal expansion coefficient more meets the requirements, while overcoming aluminium-using heat-resisting, anti-corrosion, high electric insulation and high-strength glass ceramics lantern ring The conductivity problems of low temperature sealing glass;
3) the utility model uses heat-resisting, anti-corrosion, high electric insulation, high expansion and high-strength glass ceramics washer, and makes it Surface coats anti-corrosion low temperature sealing glass, not only can control aluminium cover plate at a distance from pole pedestal, but also can be further improved sealing-in The air-tightness and structural integrity of part;
Detailed description of the invention
Fig. 1 is the sectional view of the glass-sealed seal assembly of the utility model aluminum hull power battery electrode pole;
Fig. 2 is the section that the glass-sealed seal assembly of the utility model aluminum hull power battery electrode pole is covered containing annulus Figure;
Fig. 3 is sectional view of the glass-sealed seal assembly of the utility model aluminum hull power battery electrode pole containing top layer;
Fig. 4 is section of the glass-sealed seal assembly of the utility model aluminum hull power battery electrode pole containing sealing ring Figure;
Fig. 5 is another sectional view of the glass-sealed seal assembly of the utility model aluminum hull power battery electrode pole;
Fig. 6 is the cathode seal assembly of the glass-sealed seal assembly of the utility model aluminum hull power battery electrode pole;
Fig. 7 is that a kind of phosphate glass is formulated corresponding thermal dilatometry.
Wherein:
1- electrode stem, 2- electrodes base, 3- battery cover board, 4- seal glass, 41- lantern ring, 42- inner coating, 43- are applied outside Layer, 5- washer, 6- annular convex platform, 7- annulus set, 8- top layer, 9- sealing ring.
Specific embodiment
It is illustrated below in conjunction with preferred embodiment of the attached drawing to the utility model, it should be understood that described herein excellent It selects embodiment to be only used for describing and explaining the present invention, is not used to limit the utility model.
As shown in Figure 1, the glass-sealed seal assembly of the utility model aluminum hull power battery electrode pole, including electrode cores Column 1, electrodes base 2, battery cover board 3, seal glass 4.The seal glass 4 includes lantern ring 41, inner coating 42 and external coating 43.It should Electrode stem 1 is set on the electrodes base 2, which is equipped with through-hole corresponding with the electrode stem 1.It should Battery cover board 3 passes through the electrode stem 1 and is located on the electrodes base 2.
The lantern ring 41 is sheathed on the electrode stem 1, and lantern ring 41 is located at the electrode stem 1 and the battery cover board Between 3.The inner coating 42, the external coating 43 are coated on the internal diameter and outer diameter of the lantern ring 41, and the inner coating 42 It is close to the outer diameter setting of the electrode stem 1, the external coating 43 is close to the through-hole setting of the battery cover board 3.
The cross sectional shape of the lantern ring 41 is arbitrary shape such as rectangle, containing concave-convex curved surface or corrugated rectangle or the bottom of containing Portion's step " T " or L shape, the longest length of straight line is by 3 through-hole diameter of battery cover board and electricity in sectional area size or face The limitation of 1 outer diameter of pole piece column.
The glass-sealed seal assembly of aluminum hull power battery electrode pole further includes washer 5, and the washer 5 passes through the electricity Pole piece column 1 is located on the electrodes base 2, and is located under the inner coating 42, the battery cover board 3.
The glass-sealed seal assembly of aluminum hull power battery electrode pole further includes annular convex platform 6, and the annular convex platform 6 is set It is placed on the battery cover board 3, and is connect with 3 integral type of battery cover board.
As shown in Fig. 2, the glass-sealed seal assembly of the utility model aluminum hull power battery electrode pole, including electrode cores Column 1, electrodes base 2, battery cover board 3, seal glass 4.
The seal glass 4 includes lantern ring 41, inner coating 42 and external coating 43.The battery cover board 3 is equipped with and the electrode The corresponding through-hole of stem 1.The electrode stem 1 is set on the electrodes base 2, and the battery cover board 3 passes through the electrode cores Column 1 is located on the electrodes base 2.
The lantern ring 41 is sheathed on the electrode stem 1, and lantern ring 41 is located at the electrode stem 1 and the battery cover board Between 3;The inner coating 42, the external coating 43 are coated on the internal diameter and outer diameter of the lantern ring 41, and the inner coating 42 It is close to the outer diameter setting of the electrode stem 1, the external coating 43 is close to the through-hole setting of the battery cover board 3.
The glass-sealed seal assembly of aluminum hull power battery electrode pole further includes washer 5, and the washer 5 passes through the electricity Pole piece column 1 is located on the electrodes base 2, and is located under the inner coating 42, the battery cover board 3.Annular convex platform 6 is set to On the battery cover board 3, and it is connect with 3 integral type of battery cover board.Aluminum hull power battery electrode pole is glass-sealed close Sealing assembly further includes annulus set 7, and the annulus set 7 passes through the electrode stem 1 and is set on the battery cover board 3, and annulus The internal diameter of set 7 is identical as the outer diameter of the annular convex platform.
Containing at least one by the flanging bore that is stamped to form, the height of flange is sufficient for sealing the battery cover board 3 that Fig. 2 is used Connect the requirement of glass contact area.But if the wall thickness of flange is inadequate, and the shape of flange is not exclusively cylinder-shaped or taper barrel, So needing that flange is modified as cylinder-shaped or taper barrel by mach method.While in order to improve the thickness of flanging bore Degree needs in addition to process the annulus set 7 of aluminum or stainless steel material or the annulus set 7 containing conical bore, the side cooperated by surplus Annulus set 7 or the annulus containing conical bore are covered 7 sets on the flanging bore processed by the method for cold extrusion by method.
As shown in figure 3, including electrode stem 1, electrodes base 2, battery cover board 3, seal glass 4;The seal glass 4 Including lantern ring 41, inner coating 42 and external coating 43;The battery cover board 3 is equipped with through-hole corresponding with the electrode stem 1;Electricity Pole piece column 1 is set on the electrodes base 2, and the battery cover board 3 passes through the electrode stem 1 and is located at the electrodes base 2 On;The lantern ring 41 is sheathed on the electrode stem 1, and lantern ring 41 be located at the electrode stem 1 and the battery cover board 3 it Between;The inner coating 42, the external coating 43 are coated on the internal diameter and outer diameter of the lantern ring 41, and the inner coating 42 is close to The outer diameter of the electrode stem 1 is arranged, and the external coating 43 is close to the through-hole setting of the battery cover board 3.
The glass-sealed seal assembly of aluminum hull power battery electrode pole further includes washer 5, and the washer 5 passes through the electricity Pole piece column 1 is located on the electrodes base 2, and is located under the inner coating 42, the battery cover board 3.Annular convex platform 6 is set to On the battery cover board 3, and it is connect with 3 integral type of battery cover board.Aluminum hull power battery electrode pole is glass-sealed close Sealing assembly further includes top layer 8, and the top layer 8 is set on the seal glass 4.
Electrode terminal seal assembly has enough structural stabilities in the transverse direction of electrode stem 1, but in 1 axis of electrode stem To, from 1 end face of electrode stem to the direction of electrodes base 2, structural stability depends on the interface bond strength of seal glass 4, In order to further put only 4 surface of seal glass by external scuffing or wound, cover and protect using a kind of plastic top 8 Shield, such as the epoxy resin bought in the market can be used, above-mentioned plastics are realized with the use of curing agent appropriate and catalyst The preparation of top layer 8;Plastic top 8 can also use other thermoplastics, for example, polyethylene, fluorubber, in 200 DEG C or less energy Cured organic silicone oil etc..
As shown in figure 4, including electrode stem 1, electrodes base 2, battery cover board 3, seal glass 4;The seal glass 4 Including lantern ring 41, inner coating 42 and external coating 43;The battery cover board 3 is equipped with through-hole corresponding with the electrode stem 1;Electricity Pole piece column 1 is set on the electrodes base 2, and the battery cover board 3 passes through the electrode stem 1 and is located at the electrodes base 2 On;The lantern ring 41 is sheathed on the electrode stem 1, and lantern ring 41 be located at the electrode stem 1 and the battery cover board 3 it Between;The inner coating 42, the external coating 43 are coated on the internal diameter and outer diameter of the lantern ring 41, and the inner coating 42 is close to The outer diameter of the electrode stem 1 is arranged, and the external coating 43 is close to the through-hole setting of the battery cover board 3.
The glass-sealed seal assembly of aluminum hull power battery electrode pole further includes washer 5, and the washer 5 passes through the electricity Pole piece column 1 is located on the electrodes base 2, and is located under the inner coating 42, the battery cover board 3.Aluminum hull power battery electricity Pole glass-sealed seal assembly in pole includes sealing ring 9, and the sealing ring 9 passes through the electrode stem 1 and is set to the electricity On pond cover board 3, and the internal diameter of sealing ring 9 is identical as the diameter of the through-hole.
Battery cover board 3 is the plane aluminum or aluminum alloy plate of relatively thin (thickness is less than 3mm), the inner wall of the through-hole on battery cover board Finite surface area constrains the interface cohesion area with seal glass 4, is unfavorable for forming solid and reliable air-tightness glass envelope It connects, it is therefore necessary in addition add the aluminum or aluminum alloy sealing ring 9 adaptable with the through-hole on cover board, which contains one The lower surface of interior round tube hole, sealing ring 9 will want parallel with 3 contact surface of battery cover board or be fitted close, and sectional area is preferentially " L " shape or step can be fixed on or be welded in advance on the outer surface of plane cover board battery cover board 3 (relative to inside battery), It is also possible to simply overlay on battery cover board 3.
Battery cover board 3 is the entire full panel of battery end-face, and thickness is thin, and the raising of 4 faying face of seal glass needs aluminium The sealing ring 9 of matter;It is different, cylindrical-opening of the battery cover board 3 used in Fig. 1 containing a heavy wall pipe projecting height, Insertion and glass electrical isolation airtight sealing, the wall thickness of cylindrical-opening to electrode stem 1 will be similar to or be greater than electrode cores The radius of column 1, to generate enough compressing forces to seal glass or to constitute the appropriate buffering impacted to external force or heat.
As shown in figure 5, the glass-sealed seal assembly of aluminum hull power battery electrode pole, including electrode stem 1, electrode bottom Seat 2, battery cover board 3, seal glass 4;The seal glass 4 includes lantern ring 41, inner coating 42 and external coating 43;The battery cover Plate 3 is equipped with through-hole corresponding with the electrode stem 1;Electrode stem 1 is set on the electrodes base 2, the battery cover Plate 3 passes through the electrode stem 1 and is located on the electrodes base 2;The lantern ring 41 is sheathed on the electrode stem 1, and is covered Ring 41 is between the electrode stem 1 and the battery cover board 3;The inner coating 42, the external coating 43 are coated on described On the internal diameter and outer diameter of lantern ring 41, and the inner coating 42 is close to the outer diameter setting of the electrode stem 1, and the external coating 43 is tight Paste the through-hole setting of the battery cover board 3.
The glass-sealed seal assembly of aluminum hull power battery electrode pole further includes washer 5 and annular convex platform 6, and washer 5 is worn It crosses the electrode stem 1 to be located on the electrodes base 2, and is located under the battery cover board 3;Annular convex platform 6 is set to described On battery cover board 3, and it is connect with 3 integral type of battery cover board.
The inner hole wall of heat resisting gasket 5 is not in close contact with 1 outer surface of electrode stem, but can be with the bottom surface of seal glass 4 Part contact is done, in the case where relatively good, the diameter of bore of heat resisting gasket 5 is identical as the diameter of bore of battery cover board 3.
Fig. 6 is the glass sealing structural schematic diagram of negative electrode pole, and distinctive points are copper electrodes pedestal 2, it with The connection of aluminum electrode stem 1 is realized by friction welding technological, and the selection of electrode stem 1, electrodes base 2 is according to battery The requirement of electrode chemical reaction determines.Since the thermal expansion coefficient of 4 system of seal glass is (16-19) * 10-6/ DEG C, with copper electricity Pole pedestal 2 relatively, 5 material of washer include the seal glass 4 on washer 5 can be with above-mentioned Positive Poles sealing used Material it is the same.
Lantern ring 41 is made of the glass ceramics of heat-resisting, high expansion, electrolyte resistance corrosion, preferably with resistance to 600 DEG C or more Glass, ceramics, glass ceramics or the glass based composite material of high temperature.Mainly hydrofluoric acid corrosion resistance is with phosphate glass The glass ceramics or glass composite material of matrix, the ceramic enhancement phase in composite material can be aluminium oxide, magnesia or nitridation Aluminium equal strength height and the good ceramic compound of thermal conductivity, content are less than 15wt%, and granularity can be Nano grade to being less than 30 microns, the advantages of shape can be spherical, whisker or sheet, this kind of structure, is improves the thermal conductivity of interface and reduces residual Waste heat stress makes not will form arc-shaped crackle around electrode stem 1 but in glass, and then improves glass sealing material The ability of thermal shock resistance and cold-and-heat resistent circulation.
The inner coating 42 and external coating 43 are made of aluminum metal-low temperature sealing glass composite material, in the preparation, wherein Aluminum metal can be fine aluminium, aluminium alloy, aluminum alloy welding feed powder, granular size can be 30 microns of nanometer, and shape can be Spherical, whisker or sheet, content can be 0.1%-99.9% in mass ratio.Inner coating 42 or external coating 43 can individually be made Standby to prepare with 4 integralization of glass ceramics lantern ring, preparation method includes but is not limited to powder compact-sintering process, glass Glass slurry the tape casting and impregnating slurry or slurry casting method etc..The advantages of this kind of structure is to make to be electrically insulated Leakless sealing more Add reliable and secure.
Coat is arranged in 5 upper surface of washer, and coat has heat-resisting, corrosion resistant effect.Lantern ring 41 and coat Material is identical.Coat is relatively thin, and thickness is less than 0.5mm.
The washer 5 is that its circular or any other shapes containing a circular through hole upper and lower surface are wanted parallel or had flat The step or groove in row face, cross section can be rectangle, square, trapezoidal, step etc., and the diameter of interior round tube hole is wanted It is greater than or is approximately equal to the diameter (such as 5-20mm) of electrode stem 1, with a thickness of 1-10mm.The making material of heat resisting gasket 5 must There must be high thermal expansion coefficient, such as in (15-23) * 10-6/ DEG C, so high thermal expansion coefficient be in order to high expansion coefficient The electrodes base 2 of aluminum or aluminum alloy sealed cell cover board 3 and high expansion coefficient matches, and otherwise will generate makes sealing-in glass The excessively high residual thermal stress of glass cracking.
Above-mentioned inner coating, the external coating are made of phosphate glass powder, and the surface of the washer coats the phosphoric acid Salt glass powder;The ingredient of the phosphate glass powder includes component in mass ratio: 47%-60%P2O5, 5%-12%Al2O3, 2%-5% B2O3, 8%-15%K2O, 5%-10%Na2O, 0.5%-5%Li2O, 1%-5%TiO2, 0.5%-3%CaF2, 0.5% -3%ZnO, 0-8%BaO, 0.5%-3%La2O3, 0.5%-3%Er2O3, 0-0.5%Nb2O5, 0.1%-3% Cr2O3, 0.1% -2%Bi2O3, 0.5%-2%V2O5, 0.5%-5%Fe2O3, 0.1%-3%Sb2O3, 0-20%PbO.The phosphorus Silicate glass powder has the characteristic of water resistant, the corrosion of acidproof and resistance to lithium-ion battery electrolytes, and its thermal expansion coefficient is (16- 19)*10-6/ DEG C, the characteristics such as half nodularization temperature or melting temperature are 500 DEG C -580 DEG C, and electrical insulating property is good.
The phosphate glass powder further includes Al in mass ratio2O3, CaF2, MgO, AlN wait additions phase, and total mass ratio is not More than 50%, for making lantern ring 41.Because lantern ring 41 has the requirement of high temperature resistant (being greater than 580 DEG C) and the requirement of Strengthening and Toughening, So needing to add one or more ceramic phases into phosphate glass matrix: the good aluminium nitride of thermal conductivity, thermal expansion coefficient are high With the calcirm-fluoride and tabular alumina of hydrofluoric acid resistant, ball-aluminium oxide etc., content is not higher than 50% (mass ratio).
In order to improve the intensity, heat resistance, the ability of fracture toughness and heat shock resistance of the seal glass, can add thermally conductive Property good aluminium nitride, keep calcirm-fluoride that thermal expansion coefficient significantly reduces and hydrofluoric acid resistant and some ceramics enhancings to increase Tough dose of such as tabular alumina, ball-aluminium oxide, the total content of above-mentioned additive can be less than common non-pressure sintering technology 15% (mass ratio), and if the total content of additive can be greater than 15% with hot-pressing sintering technique.This softening point or Higher melting-point seal glass composite material can be used to make above-mentioned glass ceramics lantern ring 41 and above-mentioned heat resisting gasket 5。
Certainly, within the scope of above-mentioned glass formula, sealing temperature and thermal expansion coefficient are all different, so to select resistance to Any seal glass (such as larger than 600 DEG C) of erosion and high temperature resistant prepares heat resisting gasket 5 and glass ceramics lantern ring 41, and to select Any seal glass (such as less than 600 DEG C) of anti-corrosion but low temperature is come the coat and above-mentioned aluminum metal-low temperature on heat resisting gasket 5 processed Glass matrix in seal glass composite material.
The composition range of phosphate glass system corresponds to unlimited kind of glass or glass ceramics or devitrified glass, wherein some glass Glass softening temperature is higher, and some is higher than 600 DEG C, and some is lower than 560 DEG C, and thermal expansion coefficient is selected to be higher than 16*10-6/ DEG C, and it is hydrogen resistant The glass formula of fluoric acid corrosion.The standard of hydrofluoric acid corrosion resistance are as follows: in the 1%HF solution of 100ml capacity, by 6 grams or so Button shape sample is placed on wherein, is impregnated 24 hours at room temperature, is then taken out sample, with pure water foam washing, then sample Product drying, claims its weight, compared with the weight before experiment, calculate weight-loss ratio, if weight-loss ratio is less than 0.5%, then it is assumed that The glass is hydrofluoric acid resistant, the electrolytic corrosion of even more resistance to lithium ion battery.
In order to prepare glass powder required for present patent application, designed according to the formula in the following table 1, using some oxides Presoma, such as use NH4H2PO4As P2O5Source, H3BO3As B2O3Source, BaCO3Source etc. as BaO, The weight of these presomas and their derivative oxides have certain proportionate relationship, such as 1.621 grams of NH4H2PO4It can obtain Obtain 1 gram of P2O5, 1.776 grams of H3BO31 gram of B can be produced2O3, 1.287 grams of BaCO3Form 1 gram of BaO etc..
1 phosphate glass formula examples of table
Wt% XG07 XG08 XG09 XG10 XG11 XG12
P2O5 60.00 52.50 47.00 48.60 55.10 47.50
B2O3 3.00 3.00 4.90 3.90 3.90 3.50
CaF2 2.00 0.50 2.00 1.00 1.00
TiO2 1.50 0.25 1.50 0.50 0.50
BaO 0.00 7.95 0.00 0.00 0.00
Na2O 5.00 6.30 7.50 7.50 7.00 7.78
K2O 13.00 14.00 14.00 12.00 13.00 14.19
Al2O3 6.00 6.50 7.00 10.00 8.00 10.23
Fe2O3 2.00 2.00 5.00 5.00 3.00
PbO 5.60 7.00 4.00 14.80
Bi2O3 2.00 1.50 2.00 2.00 2.00 2.00
Li2O 2.00 2.50 0.50 0.50 0.50
Nb2O5 0.50 0.50
V2O5 1.00 0.50 0.50 0.50
Sb2O3 0.50 0.50 0.50 0.50 0.50
Cr2O3 0.50 0.50 1.00 0.50 0.50
La2O3 1.00 0.50 0.50 0.50
ZnO 0.00 1.00 0.00 0.00
Er2O3 1.00 0.00 0.00 0.00 0.00 0.00
Total amount 100.00 100.00 100.00 100.00 100.00 100.00
Experiment discovery, due to NH4H2PO4Dosage is larger, and melt when smelting glass in crucible can be excessive, influence formula at Divide the yields with product, is unfavorable for producing in batches.So using sodium metaphosphate (NaPO3), potassium metaphosphate (KPO3), metaphosphoric acid Aluminium etc. completely or partially replaces ammonium dihydrogen phosphate, sodium carbonate (Na2CO3), potassium carbonate, aluminium oxide etc..
After weighing ingredient, dry grinded under conditions of 250 revs/min, 3 hours using planetary ball mill, Zhi Houyong Corundum or platinum crucible contain mixture, are then warming up to 1250-1350 DEG C, heat preservation 1-2 hours with 4-5 hours, then take out earthenware Crucible.Glass precursor solution therein is poured into pure water;Drying, dry grinding, screening, green compact (under the conditions of binder), dumping, Sintering or/and processing.
During the experiment, to survey glass material frit density and blank sintering density, survey melt casting after or green body The thermal dilatometry (as shown in Figure 7) of the sintered sample of semi-molten, the corrosion resistance for then surveying glass includes water-resistance, finally The mechanical performance for surveying glass material includes three-point bending strength.One disadvantage of experiment discovery phosphate glass is exactly the curved of it Qu Qiangdu is lower, is not higher than 50MPa.
(such as polyethylene glycol, molecular weight are easy less than 4000 450 for phosphate glass powder, aluminum metal powder, organic binder DEG C or less dumping it is clean), paraffin wax emulsions release agent etc. be uniformly mixed with alcohol equal solvent, slurry is made or granulation is further made Powder;Then aluminum metal-low temperature sealing glass composite material difference can be made by green compact and the method for sintering with pelletizing The tubular glass precast body of size, then with the concentric suit of glass ceramics lantern ring 41;Or pass through the side of curtain coating with above-mentioned slurry Method prepares flexible cast sheet, and the cast sheet of suitable thickness and size (can multiple-layer stacked) is then covered in above-mentioned glass ceramics set On the surfaces externally and internally of ring 41;Or the surfaces externally and internally of glass ceramics lantern ring 41 is set to coat one layer of aluminium gold with the method for impregnating slurry Category-low temperature sealing glass composite material, perhaps with the method for coaxial co-extrusion pressure or with the method etc. of multi-functional 3D printing.
A kind of method for sealing of the glass-sealed seal assembly of aluminum hull power battery electrode pole, comprising steps of
1) it assembles: the washer 5 of applying phosphate glass powder is passed through into the upper table that electrode stem 1 is located at the electrodes base 2 Lantern ring 41, inner coating 42 and external coating 43 are socketed and are placed on washer 5 by face;
2) above-mentioned seal assembly sealing-in: is put into the sealing-in in air or protective atmosphere of Muffle furnace or chain-conveyer furnace, sealing-in For temperature less than 600 DEG C, sealing time is less than 1h;Lantern ring, inner coating and external coating are transformed into mecystasis from molten state, pass through Transition temperature becomes rigid solid state.
In the highest temperature zone of sealing-in, only low temperature sealing glass starts fusing, infiltrates contacted surface and metalwork The oxide layer on surface and the oxide on glass-ceramic surface form ionic bond or/and the chemical interface of covalent bond combines, and could produce Raw good air-tightness.Sealing-in for the negative pole containing copper electrodes base 2, or the same furnace for positive and negative electrode pole Glass sealing is then needed using nitrogen, to place the excessive surface oxidation of copper electrodes pedestal 2.
After the glass sealing of high-temperature region, seal glass will be cooled to room temperature by program, and glass is from molten state during this It is changed into mecystasis, then becomes rigid solid state by glass transformation temperature.If seal glass or its compound glass The thermal expansion coefficient of glass material is not high enough, cannot match with the thermal expansion coefficient of the aluminum or copper material that are contacted, together It, cannot be with the thermal expansion coefficient phase of the seal glass contacted if the thermal expansion coefficient of sample temperature resistant encapsulation washer 5 is not high enough Matching.The mismatch of interface thermal expansion coefficient, which will lead to remnants in seal glass the most fragile in seal assembly, thermal stress, If this residual thermal stress is higher than the intensity of seal glass, such as it is higher than 50MPa, then seal glass will crack, to lead Cause the air-tightness failure of electrode seal.Further, since the good aluminum metal additive of thermal conductivity is added in seal glass, So the heat conductivity of seal glass can be improved, the poor (interface two of interface temperature generated because being quickly heated or cooled is reduced Sidepiece part heated is cooled asynchronous) and interfacial thermal stress, so be conducive to electrode seal assembly thermal shock resistance and The test of cold-resistant thermal cycle.
In order to solve main problem existing for aluminium-lead glass sealing-in, the utility model improves low temperature using aluminum disperse phase The intensity and toughness of seal glass, while using high-strength, high electric insulation, heat resistant glass-ceramic structure plug-in unit of high thermal expansion, it leads Cause interface cohesion secured, interfacial thermal stress reduces, so that the heat shock resistance and mechanical shock resistance of glass sealing component obtain Improve.
The above descriptions are merely preferred embodiments of the present invention, not makees in any form to the utility model Limitation, therefore it is all without departing from the content of the technical scheme of the utility model, implement according to the technical essence of the utility model to above Any modification, equivalent variations and modification, are still within the scope of the technical solutions of the present invention made by example.

Claims (7)

1. a kind of glass-sealed seal assembly of aluminum hull power battery electrode pole, it is characterised in that: including electrode stem, electrode Pedestal, battery cover board, seal glass;Electrode stem is set on the electrodes base, and the battery cover board passes through the electrode Stem is located on the electrodes base;The battery cover board is equipped with through-hole corresponding with the electrode stem;
The seal glass includes lantern ring, inner coating and external coating;
The lantern ring is sheathed on the electrode stem, and lantern ring is between the electrode stem and the battery cover board;Institute State inner coating, the external coating is coated on the internal diameter and outer diameter of the lantern ring, and the inner coating is close to the electrode stem Outer diameter setting, the external coating be close to the battery cover board through-hole setting.
2. the glass-sealed seal assembly of aluminum hull power battery electrode pole according to claim 1, it is characterised in that: also Including washer, the washer passes through the electrode stem and is located on the electrodes base, and is located at the inner coating, the battery Under cover board;Coat is arranged in washer face.
3. the glass-sealed seal assembly of aluminum hull power battery electrode pole according to claim 2, it is characterised in that: also Including annular convex platform, the annular convex platform is set on the battery cover board, and is connect with the battery cover board integral type.
4. the glass-sealed seal assembly of aluminum hull power battery electrode pole according to claim 3, it is characterised in that: also Including annulus set, the annulus set is set on the battery cover board across the electrode stem, and the internal diameter of annulus set and institute The outer diameter for stating annular convex platform is identical.
5. the glass-sealed seal assembly of aluminum hull power battery electrode pole according to claim 3, it is characterised in that: also Including top layer, the top layer is set on the seal glass.
6. the glass-sealed seal assembly of aluminum hull power battery electrode pole according to claim 2, it is characterised in that;Also Including sealing ring, the sealing ring passes through the electrode stem and is set on the battery cover board, and the internal diameter of sealing ring and institute The diameter for stating through-hole is identical.
7. the glass-sealed seal assembly of aluminum hull power battery electrode pole according to claim 1, it is characterised in that: also Including washer and annular convex platform, the washer passes through the electrode stem and is located on the electrodes base, and is located at the battery Under cover board;The annular convex platform is set on the battery cover board, and is connect with the battery cover board integral type.
CN201821794411.2U 2018-11-01 2018-11-01 A kind of glass-sealed seal assembly of aluminum hull power battery electrode pole Active CN209045627U (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109256499A (en) * 2018-11-01 2019-01-22 中澳科创(深圳)新材料有限公司 A kind of glass-sealed seal assembly of aluminum hull power battery electrode pole and its method for sealing

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109256499A (en) * 2018-11-01 2019-01-22 中澳科创(深圳)新材料有限公司 A kind of glass-sealed seal assembly of aluminum hull power battery electrode pole and its method for sealing
CN109256499B (en) * 2018-11-01 2023-08-11 深圳中傲新瓷科技有限公司 Sealing assembly for sealing electrode post glass of aluminum shell power battery and sealing method thereof

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