CN114267885A - Anti-drop steel shell button battery and preparation method and application thereof - Google Patents
Anti-drop steel shell button battery and preparation method and application thereof Download PDFInfo
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- CN114267885A CN114267885A CN202111574619.XA CN202111574619A CN114267885A CN 114267885 A CN114267885 A CN 114267885A CN 202111574619 A CN202111574619 A CN 202111574619A CN 114267885 A CN114267885 A CN 114267885A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910000831 Steel Inorganic materials 0.000 title claims description 10
- 239000010959 steel Substances 0.000 title claims description 10
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000003292 glue Substances 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000011888 foil Substances 0.000 claims description 29
- -1 polyphenylpropylene Polymers 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 238000003475 lamination Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- NMYFVWYGKGVPIW-UHFFFAOYSA-N 3,7-dioxabicyclo[7.2.2]trideca-1(11),9,12-triene-2,8-dione Chemical compound O=C1OCCCOC(=O)C2=CC=C1C=C2 NMYFVWYGKGVPIW-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 6
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910021384 soft carbon Inorganic materials 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 229920003051 synthetic elastomer Polymers 0.000 claims description 5
- 239000005061 synthetic rubber Substances 0.000 claims description 5
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 4
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 4
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 4
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 4
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002000 Electrolyte additive Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000002390 adhesive tape Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004804 winding Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 69
- 239000004798 oriented polystyrene Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 3
- 229920000800 acrylic rubber Polymers 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000007765 extrusion coating Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Secondary Cells (AREA)
Abstract
The invention provides a drop-resistant button cell and a preparation method and application thereof. The button battery comprises a battery shell, a battery core and composite glue positioned between the battery shell and the battery core; the composite glue comprises a substrate layer and at least one soft expansion material layer, wherein the substrate layer and the soft expansion material layer are bonded through a first glue layer, and the adjacent soft expansion material layer is bonded through a second glue layer; the material of the soft expansion material layer comprises OPS. The improved adhesive tape has a great buffer effect on the internal winding core pole piece in the falling process, so that the winding core pole piece is not broken.
Description
Technical Field
The invention relates to the field of consumer TWS earphone batteries, and relates to a drop-resistant button battery and a preparation method and application thereof.
Background
At present, PEI and PI adhesive tape that steel-shell button cell used are the relative harder sticky tape, especially after toasting, the hardness of adhesive tape is more increaseed, can't play the effect of the inside book core of protection in the in-process that falls, it is very unfavorable in the drop test to electric core, along with steel-shell button cell's cylinder performance requirement is higher and higher, simultaneously in high-end customer test procedure, use present conventional PEI and PI adhesive tape cylinder test unable to pass through, can't satisfy high-end TWS earphone manufacturer's harsh requirement, in order to improve cylinder drop test performance, development inflation adhesive tape is compelled at eyelash, mainly play the impact of buffering book core in the cylinder drop test, reach the purpose that the battery can also normally charge and discharge and do not become invalid.
CN105950043A discloses an adhesive tape for improving the drop resistance of a battery and a manufacturing method thereof. The battery comprises a five-layer structure, wherein the first layer is a pressure-sensitive adhesive with cohesiveness at normal temperature, the second layer is a base material, the third layer is a bottom gluing layer, the fourth layer is an adhesive layer, the fifth layer is a double-sided release layer, and the five-layer glue is matched for use to achieve the anti-falling effect, but the preparation process of the five-layer glue is complicated, the production cost is high, and the battery can be thickened due to the multiple layers of glue.
CN212640355U discloses a protection glue and anti lithium ion battery that falls for lithium ion battery is anti, including two-layer glue, be respectively from type rete and electrolyte-resistant glue film layer, electrolyte-resistant glue film layer sets up the space at the protection glue, can bond by a large scale during the rubberizing, but the size in space is difficult to set up, and the space is too big or too little, and the rubberizing adhesion force is not strong, consequently, the inconsistent problem of product batch effect appears easily in the preparation process.
How to prepare a drop-resistant button cell on a large scale at low cost is an important research direction in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a drop-resistant button cell with a steel shell and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a steel shell button battery, which comprises a battery shell, a battery core and a composite adhesive between the battery shell and the battery core.
The composite glue comprises a substrate layer and at least one soft expansion material layer, wherein the substrate layer and the soft expansion material layer are bonded through a first glue layer, and adjacent soft expansion material layers are bonded through a second glue layer.
The material of the soft expansion material layer comprises OPS.
The invention improves the anti-falling capability of the button cell by arranging the multilayer composite adhesive, wherein the hardness of the basal layer is higher, so that better framework supporting force of a steel shell button cell roll core can be provided, and the tail adhesive tape can well fix the roll core and can not disperse the roll core. The soft expansion material layer has good flexibility, can be better for the effect that inside roll core played buffer protection when the cylinder falls, main raw materials OPS (oriented polystyrene film, a through stretching oriented polystyrene) meets electrolyte, molecular orientation stress release, the molecular chain shrink, the unchangeable area of volume reduces, thickness increases.
As a preferred embodiment of the present invention, the raw material of the soft expansion material layer further includes any one or a combination of at least two of PS, PE, PP, modified PS, modified OPS, polyphenylpropylene, polyphenylbutylene, polyphenylpentene, polyphenylphenylene, polyphenylheptene, or polyphenyldodecene, and the combination is typically but not limited to: combinations of PS and PE, PE and PP, PP and modified PS, modified PS and modified OPS, modified OPS and polyacrylic acid, polyphenylpropylene and polyphenylbutylene, polyphenylbutylene and polyphenylpentene, polyphenylhexylene and polyphenylheptene, or polyphenylheptylene and polyphenyldodecene, and the like.
The modified PS and modified OPS of the present invention include modification by stretching. The composite material of the invention has better flexibility by using OPS and other materials as the mixed material, and can better play a role in buffering and protecting the inner winding core in the falling process of the roller.
Preferably, the substrate layer comprises any one of ethylene terephthalate, trimethylene terephthalate, butylene terephthalate, ethylene terephthalate diacetate, ethylene terephthalate dipropionate, trimethylene terephthalate, or polyimide, or a combination of at least two thereof, wherein typical but non-limiting examples are: combinations of ethylene terephthalate and trimethylene terephthalate, combinations of trimethylene terephthalate and tetramethylene terephthalate, combinations of ethylene terephthalate and ethylene terephthalate dipropionate, combinations of ethylene terephthalate and trimethylene terephthalate, or combinations of trimethylene terephthalate and polyimide, and the like.
Preferably, the mass of the base layer material accounts for 15-80% of the total mass of the compound adhesive, wherein the mass fraction of the PET may be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 55%, 60%, 65%, 70%, 75%, 80%, etc., but is not limited to the enumerated values, and other non-enumerated values within the range of the enumerated values are equally applicable, preferably 15-40%.
Preferably, the thickness of the base layer is 5 to 20 μm, wherein the thickness may be 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm or 20 μm, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the OPS accounts for 10 to 60% of the total mass of the soft swelling material layer, wherein the mass fraction of the OPS may be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, or the like, but is not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 40 to 60%.
Preferably, the thickness of the soft and expandable material layer is 5 to 20 μm, wherein the thickness may be 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm or 20 μm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
As a preferred embodiment of the present invention, the raw materials of the first glue layer and the second glue layer independently comprise any one or a combination of at least two of acrylic glue, modified acrylic glue, synthetic rubber, organic pressure-sensitive glue or acrylic glue, wherein the combination is typically but not limited to: a combination of acrylic rubber and modified acrylic rubber, a combination of modified acrylic rubber and synthetic rubber, a combination of synthetic rubber and organic pressure-sensitive adhesive, a combination of organic pressure-sensitive adhesive and acrylic adhesive, and the like.
Preferably, the thickness of the first and second glue layers is 1 to 10 μm, respectively, and the thickness of the glue layer may be 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the thickness of the composite adhesive is 3 to 50 μm, wherein the thickness may be 3 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the battery cell comprises a positive plate, a diaphragm, electrolyte and a negative plate.
Preferably, the positive electrode sheet includes a positive electrode foil and a positive electrode active material coated on the positive electrode foil.
Preferably, the negative electrode sheet includes a negative electrode foil and a positive electrode active material coated on the negative electrode foil.
Preferably, the thickness of the positive electrode foil is 6 to 20 μm, wherein the thickness may be 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the thickness of the negative electrode foil is 4 to 14 μm, wherein the thickness may be 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, or 14 μm, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferred embodiment of the present invention, the positive electrode active material includes any one or a combination of at least two of lithium iron phosphate, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminum oxide, wherein the combination is typically, but not limited to, exemplified by: a combination of lithium iron phosphate and lithium cobalt oxide, a combination of lithium cobalt oxide and lithium nickel oxide, a combination of lithium nickel oxide and lithium manganese oxide, a combination of lithium manganese oxide and lithium nickel manganese oxide, a combination of lithium nickel manganese oxide and lithium nickel cobalt manganese oxide, a combination of lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminum oxide, or the like.
Preferably, the negative active material includes any one of soft carbon, hard carbon, artificial graphite, natural graphite, silicon oxy compound, silicon carbon compound, or lithium titanate, or a combination of at least two thereof, wherein the combination is exemplified by, typically but not limited to: a combination of soft carbon and hard carbon, a combination of hard carbon and artificial graphite, a combination of artificial graphite and natural graphite, a combination of natural graphite and silicon, a combination of silicon and silicon oxy compound, a combination of silicon oxy compound and silicon carbon compound, or a combination of silicon carbon compound and lithium titanate, and the like.
As a preferred embodiment of the present invention, the electrolyte includes a nonaqueous solvent, a lithium salt, and an electrolyte additive.
Preferably, the non-aqueous solvent comprises any one of vinylene carbonate, propylene carbonate or diethyl carbonate, or a combination of at least two thereof, wherein typical but non-limiting examples thereof are: a combination of vinylene carbonate and propylene carbonate, a combination of propylene carbonate and diethyl carbonate, a combination of diethyl carbonate and vinylene carbonate, or the like.
Preferably, the lithium salt includes LiPF6。
Preferably, the additive comprises any one of vinylene carbonate, fluoroethylene carbonate or vinyl sulfate or a combination of at least two thereof, wherein typical but non-limiting examples thereof are: a combination of vinylene carbonate and fluoroethylene carbonate, a combination of fluoroethylene carbonate and vinyl sulfate, or a combination of vinylene carbonate and vinyl sulfate, and the like.
The invention also aims to provide a preparation method of the steel shell button cell, which comprises the following steps:
respectively and independently melting the raw materials of the substrate layer and the soft expansion material layer to obtain a substrate layer precursor and a soft expansion material layer precursor, extruding and stretching the melted substrate layer precursor to obtain the substrate layer, and sequentially preparing glue layers and soft expansion material layers on the substrate layer at intervals to obtain composite glue;
and after the compound adhesive is coiled and baked, coiling the positive plate and the negative plate to obtain a battery core lamination, putting the battery core lamination into a battery shell, pouring electrolyte, and cooling and packaging to obtain the button battery.
In a preferred embodiment of the present invention, the temperature in the molten state is 150 to 250 ℃, wherein the temperature may be 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mixing time is 5-15 h, wherein the time can be 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature of the mixing is 150 to 250 ℃, wherein the temperature can be 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the baking temperature is 50 to 150 ℃, wherein the temperature may be 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the baking time is 15-45 min, wherein the baking time can be 15min, 20min, 25min, 30min, 35min, 40min or 45min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
The button cell of the present invention includes a formation and aging process.
Preferably, the pressure of the chemical reaction is 0.5 to 2.5Mpa, wherein the pressure may be 0.5Mpa, 0.8Mpa, 1.0Mpa, 1.2Mpa, 1.4Mpa, 1.6Mpa, 1.8Mpa, 2.0Mpa, 2.2Mpa or 2.5Mpa, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature of the chemical conversion is 25 to 100 ℃, wherein the temperature can be 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the current for the formation constant current charging is 0.01-1C, wherein the current may be 0.01C, 0.05C, 0.1C, 0.15C, 0.2C, 0.25C, 0.3C, 0.35C, 0.4C, 0.45C, 0.5C, 0.55C, 0.6C, 0.65C, 0.7C, 0.75C, 0.8C, 0.85C, 0.9C, 0.95C, or 1C, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the intermediate constant current charging cutoff voltage is 2.8-4.5V, wherein the voltage may be 2.8V, 2.9V, 3.0V, 3.1V, 3.2V, 3.3V, 3.4V, 3.5V, 3.6V, 3.7V, 3.8V, 3.9V, 4.0V, 4.1V, 4.2V, 4.3V, 4.4V, or 4.5V, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the aging is 25 to 50 ℃, wherein the temperature can be 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the aging is carried out for 6-48 h, wherein the aging can be carried out for 6h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 48h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
The K value and the electrical property of the battery can be improved through formation and aging, and meanwhile, the dropping property is improved slightly.
The invention also aims to provide application of the steel shell battery button according to one of the aims, and the button battery is applied to the field of consumer TWS earphone batteries.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
the drop resistance of the steel shell button battery prepared by the invention is obviously improved, a 1m drop test can realize that the strip of the core pole piece is continuously rolled in 300 weeks, the 500-week pass rate is more than 92%, and the roll drop pass rate is obviously improved by only 85% compared with that of a 30-week roll before the improvement.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a preparation method of a drop-resistant button cell, which comprises the following steps:
respectively and independently melting and mixing 30% of ethylene terephthalate material, 35% of OPS and 35% of PE at the temperature of 200 ℃ for 10 hours to obtain a substrate layer precursor and a soft expansion material layer precursor, extruding and stretching the melted substrate layer precursor by extrusion injection molding equipment to obtain a substrate layer, and sequentially preparing a glue layer which is made of acrylic glue and has the thickness of 5 microns and a soft expansion material layer which is made of acrylic glue and has the thickness of 15 microns on the substrate layer by utilizing an extrusion coating machine to obtain composite glue;
and after the compound adhesive is coiled and baked, coiling the positive plate and the negative plate to obtain a battery core lamination, putting the battery core lamination into a battery shell, pouring electrolyte, and cooling and packaging to obtain the button battery.
Wherein the anode foil is an aluminum foil with the thickness of 15 mu m, and the anode active material is lithium iron phosphate.
The negative foil is copper foil with the thickness of 8 mu m, and the negative active substance is soft carbon.
The electrolyte is LiPF (lithium ion plasma display panel) containing 80% of non-aqueous solvent propylene carbonate and 15%6And 5% vinyl sulfate.
Example 2
The embodiment provides a preparation method of a drop-resistant button cell, which comprises the following steps:
respectively and independently melting and mixing 15% of polyimide material, 7.5% of OPS and 77.5% of PP at the temperature of 250 ℃ for 5 hours to obtain a substrate layer precursor and a soft expansion material layer precursor, extruding and stretching the melted substrate layer precursor by extrusion injection molding equipment to obtain a substrate layer, and sequentially preparing two glue layers which are made of synthetic rubber and have the thickness of 1 mu m and two soft expansion material layers which are made of 5 mu m on the substrate layer at intervals by utilizing an extrusion coating machine to obtain composite glue;
and after the compound adhesive is coiled and baked, coiling the positive plate and the negative plate to obtain a battery core lamination, putting the battery core lamination into a battery shell, pouring electrolyte, and cooling and packaging to obtain the button battery.
Wherein the anode foil is an aluminum foil with the thickness of 10 mu m, and the anode active material is lithium iron phosphate.
The negative foil is copper foil with the thickness of 6 mu m, and the negative active substance is soft carbon.
The electrolyte is 80 percent of nonaqueous solvent diethyl carbonate 15 percent LiPF6And 5% vinylene carbonate.
Example 3
The embodiment provides a preparation method of a drop-resistant button cell, which comprises the following steps:
respectively and independently melting and mixing 40% of polyimide material, 40% of ethylene glycol terephthalate material, 12% of OPS and 8% of modified PE at the temperature of 150 ℃ for 15 hours to obtain a base layer precursor and a soft expansion material layer precursor, extruding and stretching the melted base layer precursor by extrusion injection molding equipment to obtain a base layer, and sequentially preparing a layer of material with the thickness of 10 microns, namely an acrylic glue layer, and a layer of soft expansion material layer with the thickness of 20 microns on the base layer by using an extrusion coating machine to obtain composite glue;
and after the compound adhesive is coiled and baked, coiling the positive plate and the negative plate to obtain a battery core lamination, putting the battery core lamination into a battery shell, pouring electrolyte, and cooling and packaging to obtain the button battery.
Wherein the anode foil is an aluminum foil with the thickness of 20 mu m, and the anode active material is lithium iron phosphate.
The negative foil is copper foil with the thickness of 10 mu m, and the negative active substance is soft carbon.
The electrolyte is LiPF (lithium ion plasma) containing 80% of non-aqueous solvent vinylene carbonate and 15%6And 5% fluoroethylene carbonate
Example 4
In this example, the thickness of the positive electrode foil was replaced with 8 μm, and the other conditions were the same as in example 1.
Example 5
In this example, the thickness of the positive electrode foil was replaced with 22 μm, and the other conditions were the same as in example 1.
Example 6
In this example, the thickness of the negative electrode foil was replaced with 4 μm, and the other conditions were the same as in example 1.
Example 7
In this example, the thickness of the negative electrode foil was changed to 12 μm, and the other conditions were the same as in example 1.
Comparative example 1
This comparative example was conducted under the same conditions as in example 1 except that no PET layer was prepared.
Comparative example 2
This comparative example was conducted under the same conditions as in example 1 except that 35% of OPS and 35% of PE were replaced with 70% of PE.
Comparative example 3
This comparative example was conducted under the same conditions as in example 1 except that the soft swelling material layer was not prepared.
The coin cells prepared in examples 1 to 7 and comparative examples 1 to 3 were subjected to a drop test at a height of 1m, and the test results are shown in table 1.
TABLE 1
| Passing rate of continuous strip of 200-cycle pole piece | Passing rate of continuous strip of 300-cycle pole piece | Energy density | |
| Example 1 | 100％ | 95％ | 350Wh/L |
| Example 2 | 100％ | 96％ | 385Wh/L |
| Example 3 | 100％ | 90％ | 332Wh/L |
| Example 4 | 100％ | 87％ | 367Wh/L |
| Example 5 | 100％ | 96％ | 297Wh/L |
| Example 6 | 100％ | 75％ | 385Wh/L |
| Example 7 | 100％ | 95％ | 360Wh/L |
| Comparative example 1 | 100％ | 97％ | 350Wh/L |
| Comparative example 2 | 100％ | 88％ | 350Wh/L |
| Comparative example 3 | 82％ | 60％ | 350Wh/L |
From the above results, it can be seen that the continuous band passing rate of the electrode sheet at 300 cycles in examples 1-3 can reach 90% or more, and at the same time, the higher energy density of the battery is maintained, the thickness of the positive electrode foil in example 4 is smaller, the continuous band passing rate of the electrode sheet at 300 cycles is lower, the thickness of the positive electrode foil in example 5 is larger, the continuous band passing rate of the electrode sheet at 300 cycles is higher, but the capacity density of the battery is lower, the thickness of the negative electrode foil in example 6 is smaller, the continuous band passing rate of the electrode sheet at 300 cycles is lower, the thickness of the negative electrode foil in example 7 is larger, the capacity density of the battery is lower, and the pure OPS is used in comparative example 1, and compared with example 1, the continuous band passing rate of the electrode sheet at 300 cycles is higher, but the hardness of the pure OPS is too small, the binding force to the battery is insufficient, and the expansion and shrinkage phenomena during the discharge of the winding core occur, so that the base layer material is compounded. Comparative example 2 can learn that the expansibility of OPS is strong, protection pole piece that can be better, in comparative example 3, does not use soft inflation material layer for roll core very easy emergence fracture when falling.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The button battery with the steel shell is characterized by comprising a battery shell, a battery core and composite glue between the battery shell and the battery core;
the composite glue comprises a substrate layer and at least one soft expansion material layer, wherein the substrate layer and the soft expansion material layer are bonded through a first glue layer, and the adjacent soft expansion material layer is bonded through a second glue layer;
the material of the soft expansion material layer comprises OPS.
2. The button cell as claimed in claim 1, wherein the material of the soft expansion material layer further comprises any one or a combination of at least two of PS, PE, PP, modified PS, modified OPS, polyphenylpropylene, polyphenylbutylene, polyphenylpentene, polyphenylphenylene, polyphenylpentylene, or polyphenyldodecene;
preferably, the substrate layer comprises any one of or a combination of at least two of ethylene terephthalate, trimethylene terephthalate, butylene terephthalate, ethylene terephthalate diacetate, ethylene terephthalate dipropionate, trimethylene terephthalate dipropionate or polyimide;
preferably, the mass of the base layer material accounts for 15-80% of the total mass of the composite adhesive, and is preferably 15-40%;
preferably, the thickness of the substrate layer is 5-20 μm;
preferably, the OPS accounts for 10-60% of the total mass of the soft expansion material layer, and preferably 40-60%;
preferably, the thickness of the soft expansion material layer is 5 to 20 μm.
3. The button cell as claimed in claim 1 or 2, wherein the raw materials of the first and second glue layers respectively and independently comprise any one or a combination of at least two of acrylic glue, modified acrylic glue, synthetic rubber, organic pressure-sensitive glue or acrylic glue;
preferably, the thicknesses of the first glue layer and the second glue layer are respectively and independently 1-10 μm;
preferably, the thickness of the compound glue is 10-50 μm.
4. The button battery according to any one of claims 1-3, wherein the battery core comprises a positive plate, a diaphragm, an electrolyte and a negative plate;
preferably, the positive plate comprises a positive foil and a positive active material coated on the positive foil;
preferably, the negative electrode sheet includes a negative electrode foil and a positive electrode active material coated on the negative electrode foil;
preferably, the thickness of the positive foil is 6-20 μm;
preferably, the thickness of the negative electrode foil is 4-14 μm.
5. The button cell according to claim 4, wherein the positive active material comprises any one of lithium iron phosphate, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminum oxide, or a combination of at least two thereof;
preferably, the negative active material includes any one of soft carbon, hard carbon, artificial graphite, natural graphite, silicon oxy compound, silicon carbon compound, or lithium titanate, or a combination of at least two thereof.
6. The button cell according to claim 4 or 5, wherein the electrolyte comprises a non-aqueous solvent, a lithium salt, and an electrolyte additive;
preferably, the non-aqueous solvent comprises any one of vinylene carbonate, propylene carbonate or diethyl carbonate or a combination of at least two of the same;
preferably, the lithium salt includes LiPF6；
Preferably, the additive comprises any one of vinylene carbonate, fluoroethylene carbonate or vinyl sulfate or a combination of at least two of the vinylene carbonate, the fluoroethylene carbonate or the vinyl sulfate.
7. A method for manufacturing a steel shell button cell according to any of the claims 1 to 6, comprising:
respectively and independently melting and mixing the raw materials of the base layer and the soft expansion material layer to obtain a base layer precursor and a soft expansion material layer precursor, extruding and stretching the melted base layer precursor to obtain the base layer, and sequentially preparing glue layers and soft expansion material layers on the base layer at intervals to obtain composite glue;
and after the compound adhesive is coiled and baked, coiling the positive plate and the negative plate to obtain a battery core lamination, putting the battery core lamination into a battery shell, pouring electrolyte, and cooling and packaging to obtain the button battery.
8. The preparation method according to claim 7, wherein the melting temperature is 150-250 ℃;
preferably, the mixing time is 5-15 h;
preferably, the temperature of the mixing is 150-250 ℃.
9. The preparation method according to claim 7 or 8, wherein the baking temperature is 50-150 ℃;
preferably, the baking time is 15-45 min.
10. Use of a steel-shelled button cell according to any one of claims 1 to 6 in the field of consumer TWS headset batteries.
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Cited By (1)
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