CN113363486A - Soft package lithium ion battery - Google Patents
Soft package lithium ion battery Download PDFInfo
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- CN113363486A CN113363486A CN202110593466.7A CN202110593466A CN113363486A CN 113363486 A CN113363486 A CN 113363486A CN 202110593466 A CN202110593466 A CN 202110593466A CN 113363486 A CN113363486 A CN 113363486A
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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
- H01M4/621—Binders
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/528—Fixed electrical connections, i.e. not intended for disconnection
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
- H01M50/533—Electrode connections inside a battery casing characterised by the shape of the leads or tabs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a soft package lithium ion battery, which comprises: the positive plate comprises a positive binder, and the mass of the positive binder accounts for 1.5-4% of the total mass of the positive active material layer; the negative plate comprises a negative current collector, and the negative current collector is a bottom-coated copper foil; the tab is respectively connected with the positive plate and the negative plate and comprises an exposed section and a connecting section, and the length of the connecting section is at least half of that of the battery; and the diaphragm is arranged between the positive plate and the negative plate and comprises a substrate layer, an insulating layer and a bonding layer, the insulating layer is arranged on at least one surface of the substrate layer, and the bonding layer is used for bonding the positive plate and the negative plate respectively. The soft package lithium ion battery provided by the invention can improve the impact performance of a heavy object, reduce short circuit points and improve the passing rate of the heavy object impact test of the soft package lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a soft package lithium ion battery.
Background
Lithium ion batteries have the advantages of light weight, good safety performance and the like, so that the lithium ion batteries are applied to the fields of mobile electronic equipment such as Bluetooth headsets, mobile phones, notebook computers, tablet computers and cameras, portable mobile power supplies and the like. Meanwhile, lithium ion batteries have also been applied in the fields of electric motorcycles, electric automobiles, and the like in batches.
One of the main shortcomings of the current soft package type lithium ion battery is poor safety performance, when the battery is damaged by mechanical external force, the battery is easy to ignite, wherein a heavy object in a UL1642 test project is an impact project, namely a simulation test that the simulation battery is damaged by mechanical external force, the conventional battery is subjected to the heavy object impact test and can ignite, the common prior art in the industry is that a waistcoat is added to a winding core, namely, an empty copper foil and an empty aluminum foil at the head or the tail of an electric core are prolonged, and the battery surrounds a half circle, a circle or more of the electric core in a period. The principle of the technology for improving the impact of the heavy object is as follows: when carrying out heavy object impact test, the short circuit can take place for electric core, and the huge joule heat that the short circuit produced can't dispel the heat well, is the root cause that leads to electric core to catch fire, and if electric core had the vest this moment, the vest short circuit (empty copper foil and empty aluminium foil short circuit promptly) is because contact resistance is very little, and the short circuit divides the electric current a lot, and most short circuit current passes through the vest, and the joule heat that the short circuit produced also is dispelled the heat by the vest. So that the heat is not concentrated, thereby achieving the purpose of improving the impact of the heavy object. However, this improvement method has the following obvious disadvantages: 1. the capacity loss is great, if the vest number of turns is few then improve the effect poor, if the vest number of turns is many, then capacity loss is big, use round vest as example (supposing copper foil thickness 6um, aluminium foil thickness 10um, diaphragm thickness 8um, then the thickness space that 64um will be lost to round vest) 2, production technology difficulty 3, increase K value.
In view of the above, it is necessary to provide a technical solution to the above technical problems.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the soft package lithium ion battery is provided, the impact performance of a heavy object can be improved, short circuit points are reduced, and the passing rate of the impact test of the heavy object of the soft package lithium ion battery is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a soft pack lithium ion battery comprising:
the positive plate comprises a positive current collector and a positive active material layer coated on the surface of the positive current collector, wherein the positive active material layer comprises a positive binder, and the mass of the positive binder accounts for 1.5-4% of the total mass of the positive active material layer;
the negative plate comprises a negative current collector and a negative active material layer coated on the surface of the negative current collector, wherein the negative current collector is a bottom-coated copper foil;
the tab is respectively connected with the positive plate and the negative plate and comprises an exposed section and a connecting section, and the length of the connecting section is at least half of that of the battery; and
the diaphragm, set up in positive plate with between the negative pole piece, the diaphragm includes substrate layer, insulating layer and tie coat, the insulating layer set up in an at least surface of substrate layer, the tie coat is used for bonding respectively positive plate with the negative pole piece.
As an improvement of the soft package lithium ion battery of the present invention, the length of the connecting segment is 3/5 or 2/3 of the length of the battery.
As an improvement of the soft package lithium ion battery, the mass of the positive electrode binder accounts for 2.5-3% of the total mass of the positive electrode active material layer.
As an improvement of the soft-package lithium ion battery of the present invention, the positive electrode binder includes at least one of polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, epoxy resin, and nylon.
As an improvement of the soft package lithium ion battery, the base coating copper foil comprises a copper foil and an adhesive base coating layer arranged on at least one surface of the copper foil, and the thickness of the adhesive base coating layer is 0.5-2 μm.
As an improvement of the soft package lithium ion battery of the present invention, the adhesion primer layer includes conductive carbon, an oily binder and an oily dispersant.
As an improvement of the soft package lithium ion battery, the conductive carbon is in a sheet shape and/or a spherical shape, the conductive carbon comprises at least one of graphene, expanded graphite, ketjen black and acetylene black, the oily binder comprises at least one of polyvinylidene fluoride, polyvinyl alcohol and polytetrafluoroethylene, and the oily dispersant comprises at least one of glycerol, triton X-100, polyvinylpyrrolidone and polyethylene glycol.
As an improvement of the soft package lithium ion battery, the substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer comprises at least one of polyethylene, polypropylene, polyethylene terephthalate and polyimide.
As an improvement of the soft-packed lithium ion battery according to the present invention, the insulating layer includes inorganic particles including at least one of alumina, silica, magnesia, titania, hafnia, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconia, yttria, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate.
As an improvement of the soft package lithium ion battery, the bonding layer comprises at least one of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.
As an improvement of the soft package lithium ion battery of the present invention, the insulating layer is disposed on a surface of the substrate layer, and the bonding layers are disposed on the surfaces of the substrate layer and the insulating layer, respectively.
Compared with the prior art, the beneficial effects of the invention include but are not limited to:
the invention improves the proportion of the anode binder, so that the adhesive property of the anode active substance layer and the anode current collector is good, and when heavy object impact occurs, the fracture appearance of the battery core is good and short circuit points are few. According to the invention, the negative current collector is replaced by the bottom-coated copper foil, so that the powder falling phenomenon of the negative active material is greatly improved, the effect of the negative active material bonded on the copper foil is good, the negative electrode at the fracture of the battery cell falls off less during the heavy object impact test, and the short circuit is reduced. The diaphragm used in the invention is provided with the bonding layer, so that the positive plate and the negative plate can be well bonded, the fracture appearance is more complete when heavy object impact occurs, and the occurrence of short circuit is reduced. The invention also prolongs the length of the lug, and the length exceeds the middle position of the battery cell in which the iron bar is placed during the heavy object impact test, so that the iron bar can be pressed on the lug. Because utmost point ear thickness is thicker, when the heavy object impact takes place, utmost point ear can not smashed the fracture, can warp, can pass through the contact short circuit between empty copper foil and the empty aluminium foil between the utmost point ear, can guide electric current and heat to pass through to improve heavy object impact property. According to the invention, the positive plate is bonded, the negative plate is bonded to the positive and negative electrodes in sequence, and the more adhesive diaphragm is used for bonding, so that short circuit points are reduced during testing, and the length of the tab is prolonged to promote short circuit between the positive and negative current collectors, so that short circuit current and heat mainly pass through the positive and negative current collectors, and the dangerous situation of short circuit heat concentration is reduced. The structures of the invention play a synergistic role in improving the impact performance of the heavy object, and finally achieve the purpose of improving the impact of the heavy object. The invention has small loss to the battery capacity and mass production capability.
Drawings
Fig. 1 is a cross-sectional view of a bottom-coated copper foil in example 1.
Fig. 2 is a sectional view of the separator in example 1.
Fig. 3 is a schematic structural diagram of a soft package lithium ion battery in embodiment 1.
Fig. 4 is a schematic structural diagram of the soft-packed lithium ion battery in comparative example 1.
In the figure: 11-copper foil, 12-bonding bottom coating, 21-substrate layer, 22-insulating layer, 23-bonding layer, 31-positive tab and 32-negative tab.
Detailed Description
The present application is further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
The invention provides a soft package lithium ion battery, which comprises:
positive plate
In the soft package lithium ion battery, the positive plate comprises a positive current collector and a positive active material layer, the material of the positive current collector comprises but is not limited to aluminum foil, and the specific type of the positive active material layer is not particularly limited and can be selected according to requirements.
In some embodiments, the positive electrode active material layer includes a positive electrode active material including a compound that reversibly intercalates and deintercalates lithium ions. In some embodiments, the positive active material may include a composite oxide containing lithium and at least one element selected from cobalt, manganese, and nickel.
In some embodiments, the positive active material is LiCowL1-wO2Wherein L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0<w≤1。
In some embodiments, the positive active material is LiNixCoyMnzM1-x-y-zO2Wherein M is selected from any one of Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is less than or equal to 1.
In some embodiments, the positive active material is LiNiaCobAlcN1-a-b-cO2Wherein N is selected from Co, Ni, Mn, Mg, Cu, Zn,Any one of Al, Sn, B, Ga, Cr, Sr, V and Ti, and a is more than or equal to 0<1，0≤b≤1，0≤c≤1，a+b+c≤1。
In still other embodiments, the positive active material is selected from lithium cobaltate (LiCoO)2) Lithium nickel manganese cobalt ternary material and lithium manganate (LiMn)2O4) Lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) Lithium iron phosphate (LiFePO)4) One or more of them.
In some embodiments, the positive electrode active material layer further includes a positive electrode binder for improving binding of the positive electrode active material particles to each other and also improving binding of the positive electrode active material to the positive electrode current collector. The positive electrode binder includes at least one of polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, and nylon.
In some embodiments, the mass of the positive electrode binder accounts for 1.5-4% of the total mass of the positive electrode active material layer. In some embodiments, the mass of the positive electrode binder accounts for 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, etc. of the total mass of the positive electrode active material layer.
In some embodiments, the mass of the positive electrode binder accounts for 2.5-3% of the total mass of the positive electrode active material layer. In some embodiments, the mass of the positive electrode binder accounts for 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, etc. of the total mass of the positive electrode active material layer.
In some embodiments, the positive electrode active material layer further includes a positive electrode conductive agent, thereby imparting conductivity to the electrode. The positive electrode conductive agent may include any conductive material as long as it does not cause a chemical change. Non-limiting examples of the positive electrode conductive agent include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., including, for example, copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives), and mixtures thereof.
Positive tab
The current for deriving the positive plate, positive ear and positive plate are connected, and positive ear includes exposes section and linkage segment, and the length of linkage segment is half of the length of battery at least.
Negative plate
In the soft package lithium ion battery of the invention, the negative plate comprises a negative current collector and a negative active material layer arranged on at least one surface of the negative current collector, and the specific type of the negative active material layer is not particularly limited and can be selected according to requirements.
The negative current collector is made of a bottom-coated copper foil, the bottom-coated copper foil comprises a copper foil and a bonding bottom coating arranged on at least one surface of the copper foil, and the thickness of the bonding bottom coating is 0.5-2 mu m. In some embodiments, the adhesion primer layer has a thickness of 0.5 μm, 1 μm, 1.5 μm, 2 μm, or the like.
In some embodiments, the adhesion primer layer includes conductive carbon, an oily binder, and an oily dispersant.
In some embodiments, the conductive carbon is in a flake and/or sphere shape, the conductive carbon includes at least one of graphene, expanded graphite, ketjen black, and acetylene black, the oily binder includes at least one of polyvinylidene fluoride, polyvinyl alcohol, and polytetrafluoroethylene, and the oily dispersant includes at least one of glycerin, triton X-100, polyvinylpyrrolidone, and polyethylene glycol.
In some embodiments, the negative active material layer includes a negative active material including artificial graphite, natural graphite, single-walled carbon nanotubes, multi-walled carbon nanotubes, mesophase micro carbon spheres (abbreviated as MCMB), hard carbon, soft carbon, silicon-carbon composites, Li-Sn alloys, Li-Sn-O alloys, Sn, SnO2Spinel-structured lithiated TiO2-Li4Ti5O12And one or more of Li-Al alloy.
In some embodiments, the anode active material layer may include an anode binder for improving the binding of the anode active material particles to each other and the binding of the anode active material to the anode current collector. Non-limiting examples of the negative electrode binder include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, epoxy, nylon, and the like.
In some embodiments, the negative electrode active material layer further includes a negative electrode conductive agent for imparting conductivity to the electrode. The negative electrode conductive agent may include any conductive material as long as it does not cause a chemical change. Non-limiting examples of the negative electrode conductive agent include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., such as copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives), and mixtures thereof.
Negative electrode tab
The negative electrode tab is connected with the negative electrode piece and comprises an exposed section and a connecting section, and the length of the connecting section is at least half of that of the battery.
Diaphragm
In the soft package lithium ion battery, a diaphragm is arranged between the positive plate and the negative plate to prevent short circuit.
In some embodiments, the separator includes a substrate layer, an insulating layer disposed on a surface of the substrate layer, and a bonding layer for bonding the positive electrode sheet and the negative electrode sheet, respectively.
In some embodiments, the substrate layer is a non-woven fabric, a film or a composite film having a porous structure, and the material of the substrate layer includes at least one of polyethylene, polypropylene, polyethylene terephthalate, and polyimide.
In some embodiments, the insulating layer comprises inorganic particles comprising at least one of alumina, silica, magnesia, titania, hafnia, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconia, yttria, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate.
In some embodiments, the tie layer comprises at least one of polyvinylidene fluoride, copolymers of vinylidene fluoride-hexafluoropropylene, polyamides, polyacrylonitriles, polyacrylates, polyacrylic acids, polyacrylates, polyvinylpyrollidones, polyvinyl ethers, polymethyl methacrylates, polytetrafluoroethylene, and polyhexafluoropropylene.
In some embodiments, the insulating layer is disposed on a surface of the substrate layer, and the adhesive layer is disposed on the surface of the substrate layer and the insulating layer, respectively.
In some embodiments, the insulating layer is disposed on both surfaces of the substrate layer, and the adhesive layers are disposed on the surfaces of the insulating layer respectively.
Electrolyte solution
The electrolyte includes a lithium salt, an organic solvent, and an additive.
In some embodiments, the lithium salt is lithium hexafluorophosphate. In some embodiments, the lithium salt is a mixed salt of lithium hexafluorophosphate and a doped lithium salt comprising at least one of lithium bis-fluorosulfonylimide, lithium bis-trifluoromethylsulfonyl imide, lithium difluoro-oxalato-borate, lithium difluorophosphate, lithium tetrafluoroborate, lithium bis-oxalato-borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium perfluoroalkyl sulfonyl imide, lithium perfluoroalkyl sulfonyl methide, lithium difluoro-oxalato-phosphate, and lithium tetrafluorooxalato-phosphate.
In some embodiments, the organic solvent comprises ethylene carbonate and diethyl carbonate. In some embodiments, the organic solvent comprises propylene carbonate and diethyl carbonate. In some embodiments, the organic solvent comprises ethylene carbonate, propylene carbonate, and diethyl carbonate.
In some embodiments, the organic solvent comprises at least one of ethyl methyl carbonate, dimethyl carbonate, propyl propionate, ethyl propionate, propyl acetate, butyl butyrate, ethyl butyrate, gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, ethyl acetate, dipropyl carbonate, and dibutyl carbonate, in addition to the organic solvents listed above.
In some embodiments, the additive comprises at least one of 1, 3-propane sultone, fluoroethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1, 3-propene sultone, 1, 4-butanesultone, triallyl isocyanurate, triallyl phosphate, ethyl 4,4, 4-trifluorobutyrate, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, fluorobenzene, boron trifluoride tetrahydrofuran, tris (trimethylsilane) phosphate, tris (trimethylsilane) borate, and methylene methanedisulfonate.
Examples
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
As shown in fig. 1 to 3, the present embodiment provides a soft package lithium ion battery, and the preparation method includes the following operations:
1) preparation of positive plate
Mixing a positive electrode active material LCO (4.48V), conductive carbon black Super-P and a binder Polytetrafluoroethylene (PTFE) according to a mass ratio of 96:1:3, and then dispersing the materials in N-methyl-2-pyrrolidone (NMP) to obtain positive electrode slurry; uniformly coating the anode slurry on two sides of an aluminum foil, and drying, rolling and vacuum drying the aluminum foil;
cutting the positive electrode tab 31, namely an aluminum tab, presetting an exposed section and a connecting section of the aluminum tab, wherein the length of the connecting section is half of the length of the positive electrode plate, and welding the connecting section of the aluminum tab with the aluminum foil by using an ultrasonic welding machine to obtain the positive electrode plate.
2) Preparation of negative plate
Mixing artificial graphite serving as a negative electrode active material, conductive carbon black Super-P, Styrene Butadiene Rubber (SBR) serving as a binder and carboxymethyl cellulose (CMC) according to a mass ratio of 94:1:2.5:2.5, and dispersing the materials in ionized water to obtain negative electrode slurry;
preparing graphene, Ketjen black, polyvinylidene fluoride and polyvinylpyrrolidone into bonding base coating slurry according to the proportion of 48:48:2:2, coating the bonding base coating slurry on two surfaces of a negative current collector copper foil 11, and drying to obtain a base coating copper foil with a bonding base coating 12 of 2 microns;
coating the negative electrode slurry on two surfaces of the bottom-coated copper foil, and drying, rolling and vacuum drying the bottom-coated copper foil;
and cutting the negative electrode tab 32, namely a nickel tab, arranging an exposed section and a connecting section of the nickel tab in advance, wherein the length of the connecting section is half of that of the negative electrode piece, and welding the connecting section of the nickel tab with the bottom-coated copper foil by using an ultrasonic welding machine to obtain the negative electrode piece.
3) Preparation of the electrolyte
Ethylene Carbonate (EC), diethyl carbonate (DEC) and Propylene Carbonate (PC) were mixed in a mass ratio of EC: DEC: PC: 2:6:2, and then 0.2 wt% VC, 5.0 wt% FEC, 2 wt% PS, 1.0 wt% ADN, 1.0 wt% EGBE and 1.0 wt% HTCN were added, respectively, followed by 14.0 wt% lithium hexafluorophosphate (LiPF)6) Fully mixing and dissolving for later use.
4) Preparation of the separator
Selecting a Polyethylene (PE) diaphragm with the thickness of 16 microns as a base material layer 21;
dissolving alumina and vinylidene fluoride-hexafluoropropylene copolymer in a N-methyl pyrrolidone solution to prepare ceramic slurry, and coating the ceramic slurry on one surface of a polyethylene diaphragm to obtain an insulating layer 22;
and dissolving oily polyvinylidene fluoride into a glue solution, coating the glue solution on the surfaces of the polyethylene diaphragm substrate layer and the insulating layer to obtain a bonding layer 23, and preparing the diaphragm.
5) Preparation of soft package lithium ion battery
Winding a sandwich structure consisting of the positive plate, the negative plate and the diaphragm, flattening the wound body, putting the flattened wound body into an aluminum-plastic film packaging bag, and baking the flattened wound body in vacuum at 80 ℃ for 48 hours to obtain an electric core to be injected with liquid; respectively injecting the prepared electrolyte into a battery cell in a glove box with the dew point controlled below-40 ℃, ensuring that the exposed sections of the aluminum lug and the nickel lug are exposed out of an aluminum plastic film packaging bag for vacuum packaging, standing for 24 hours, and then carrying out conventional formation and capacity grading according to the following steps: charging at 0.05C for 180min, charging at 0.2C to 4.0V, and vacuum sealing twice; further charging to 4.48V at a constant current of 0.2C, standing at normal temperature for 24h, and discharging to 3.0V at a constant current of 0.2C; and finally, charging the battery to 4.48V at a constant current of 1C for standby.
Example 2
The embodiment provides a soft package lithium ion battery, which is different from the embodiment 1 in that the preparation of a positive plate comprises the following steps:
a positive electrode active material LCO (4.48V), conductive carbon black Super-P and a binder polytetrafluoroethylene were mixed in a mass ratio of 96.5:2: 1.5.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The embodiment provides a soft package lithium ion battery, which is different from the embodiment 1 in that the preparation of a positive plate comprises the following steps:
a positive electrode active material LCO (4.48V), conductive carbon black Super-P and a binder polytetrafluoroethylene were mixed in a mass ratio of 95:1: 4.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The embodiment provides a soft package lithium ion battery, which is different from the embodiment 1 in that the preparation of a positive plate comprises the following steps:
a positive electrode active material LCO (4.48V), conductive carbon black Super-P and a binder polytetrafluoroethylene were mixed in a mass ratio of 96:1.5: 2.5.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
As shown in fig. 4, this embodiment provides a soft-package lithium ion battery, and the preparation method includes the following operations:
1) preparation of positive plate
Mixing a positive electrode active material LCO (4.48V), conductive carbon black Super-P and a binder Polytetrafluoroethylene (PTFE) according to a mass ratio of 97:2:1, and then dispersing the materials in N-methyl-2-pyrrolidone (NMP) to obtain positive electrode slurry; uniformly coating the anode slurry on two sides of an aluminum foil, and drying, rolling and vacuum drying the aluminum foil;
and cutting the aluminum lug, presetting an exposed section and a connecting section of the aluminum lug, wherein the length of the connecting section is one sixth of the length of the positive plate, and welding the connecting section of the aluminum lug with the aluminum foil by using an ultrasonic welding machine to obtain the positive plate.
2) Preparation of negative plate
Mixing artificial graphite serving as a negative electrode active material, conductive carbon black Super-P, Styrene Butadiene Rubber (SBR) serving as a binder and carboxymethyl cellulose (CMC) according to a mass ratio of 94:1:2.5:2.5, and dispersing the materials in ionized water to obtain negative electrode slurry;
coating the negative electrode slurry on two sides of a copper foil, and drying, rolling and vacuum drying the copper foil;
and cutting the nickel tab, arranging an exposed section and a connecting section of the nickel tab in advance, wherein the length of the connecting section is one sixth of that of the negative plate, and welding the connecting section of the nickel tab with the bottom-coated copper foil by using an ultrasonic welding machine to obtain the negative plate.
3) Preparation of the electrolyte
Ethylene Carbonate (EC), diethyl carbonate (DEC) and Propylene Carbonate (PC) were mixed in a mass ratio of EC: DEC: PC: 2:6:2, and then 0.2 wt% VC, 5.0 wt% FEC, 2 wt% PS, 1.0 wt% ADN, 1.0 wt% EGBE and 1.0 wt% HTCN were added, respectively, followed by 14.0 wt% lithium hexafluorophosphate (LiPF)6) Fully mixing and dissolving for later use.
4) Preparation of the separator
Selecting 16 mu m thick Polyethylene (PE) as a diaphragm;
5) preparation of soft package lithium ion battery
Winding a sandwich structure consisting of the positive plate, the negative plate and the diaphragm, flattening the wound body, putting the flattened wound body into an aluminum-plastic film packaging bag, and baking the flattened wound body in vacuum at 80 ℃ for 48 hours to obtain an electric core to be injected with liquid; respectively injecting the prepared electrolyte into a battery cell in a glove box with the dew point controlled below-40 ℃, ensuring that the exposed sections of the aluminum lug and the nickel lug are exposed out of an aluminum plastic film packaging bag for vacuum packaging, standing for 24 hours, and then carrying out conventional formation and capacity grading according to the following steps: charging at 0.05C for 180min, charging at 0.2C to 4.0V, and vacuum sealing twice; further charging to 4.48V at a constant current of 0.2C, standing at normal temperature for 24h, and discharging to 3.0V at a constant current of 0.2C; and finally, charging the battery to 4.48V at a constant current of 1C for standby.
Comparative example 2
The comparative example provides a soft package lithium ion battery, which is different from the embodiment 1 in the preparation of a positive plate:
a positive electrode active material LCO (4.48V), conductive carbon black Super-P and a binder polytetrafluoroethylene were mixed in a mass ratio of 96:3: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 3
The comparative example provides a soft-package lithium ion battery, which is different from the example 1 in the preparation of a negative plate:
the current collector of the negative electrode is selected from common copper foil.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 4
The present comparative example provides a soft-pack lithium ion battery, which is different from example 1 in that:
and cutting the aluminum tab, and presetting an exposed section and a connecting section of the aluminum tab, wherein the length of the connecting section is one sixth of the length of the positive plate.
And cutting the nickel tab, and arranging an exposed section and a connecting section in advance on the nickel tab, wherein the length of the connecting section is one sixth of that of the negative plate.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 5
This comparative example provides a soft-pack lithium ion battery, which differs from example 1 in the preparation of the separator:
selecting 16 mu m thick Polyethylene (PE) as a diaphragm;
the rest is the same as embodiment 1, and the description is omitted here.
Performance testing
The soft package lithium ion batteries of examples 1 to 4 and comparative examples 1 to 5 were subjected to cycle performance tests.
100 soft-packaged lithium ion batteries of examples 1 to 4 and comparative examples 1 to 5 were prepared by the same method and used for impact performance test of the weights.
And (3) testing the impact property of the weight: it is a particular practice to place the test sample cell on a flat surface. A bar cross with a root diameter of 15.8mm was placed in the center of the sample. A weight of 9.1KG was dropped from a height of 610mm onto the sample. Each sample cell can only withstand 1 impact and a different sample is used for each test. The safety performance of the battery is tested from different heavy hammers with different heights and different stress areas, and the battery is qualified after being tested according to the regulations without fire or explosion.
The test results are shown in Table 1.
TABLE 1
It can be seen from example 1 and comparative example 2 that the content of the positive electrode binder is too low, and the passing rate of the weight impact performance test is low, because the positive electrode binder is too low, the positive electrode binder cannot be tightly bonded with the positive electrode active material, and during weight impact, the fracture morphology of the positive electrode sheet is poor, and short circuit points are increased.
As can be seen from examples 1-4 and comparative examples 1-5, the pass rate of the weight impact performance test of examples 1-4 is far higher than that of comparative examples 1-5, the loss of the circulation capacity is less than 2%, and the mass production capability is realized. The soft package lithium ion battery is characterized in that the positive plate is bonded with the negative plate, and the negative plate is bonded with the positive and negative electrodes through the more adhesive diaphragms, so that short circuit points are reduced during testing, and the length of the tab is prolonged to promote short circuit between the positive and negative current collectors, so that short circuit current and heat mainly pass through the positive and negative current collectors, and the dangerous situation of short circuit heat concentration is reduced. The structures of the invention play a synergistic role in improving the impact performance of the heavy object, and finally achieve the purpose of improving the impact of the heavy object. If only a single measure is used, the improvement effect is very limited, the effect of improving the passing rate of the heavy object test can be realized only by matching, and the four measures are none.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A soft-pack lithium ion battery, comprising:
the positive plate comprises a positive current collector and a positive active material layer coated on the surface of the positive current collector, wherein the positive active material layer comprises a positive binder, and the mass of the positive binder accounts for 1.5-4% of the total mass of the positive active material layer;
the negative plate comprises a negative current collector and a negative active material layer coated on the surface of the negative current collector, wherein the negative current collector is a bottom-coated copper foil;
the tab is respectively connected with the positive plate and the negative plate and comprises an exposed section and a connecting section, and the length of the connecting section is at least half of that of the battery; and
the diaphragm, set up in positive plate with between the negative pole piece, the diaphragm includes substrate layer, insulating layer and tie coat, the insulating layer set up in an at least surface of substrate layer, the tie coat is used for bonding respectively positive plate with the negative pole piece.
2. The soft package lithium ion battery according to claim 1, wherein the mass of the positive electrode binder accounts for 2.5-3% of the total mass of the positive electrode active material layer.
3. The soft pack lithium ion battery of claim 1, wherein the positive binder comprises at least one of polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoride, polyethylene, polypropylene, styrene butadiene rubber, epoxy, and nylon.
4. The soft package lithium ion battery of claim 1, wherein the undercoat copper foil comprises a copper foil and an adhesive primer layer disposed on at least one surface of the copper foil, and the adhesive primer layer has a thickness of 0.5 to 2 μm.
5. The soft-pack lithium ion battery of claim 4, wherein the adhesion primer layer comprises conductive carbon, an oily binder, and an oily dispersant.
6. The soft-package lithium ion battery according to claim 5, wherein the conductive carbon is in a sheet shape and/or a spherical shape, the conductive carbon comprises at least one of graphene, expanded graphite, Ketjen black and acetylene black, the oily binder comprises at least one of polyvinylidene fluoride, polyvinyl alcohol and polytetrafluoroethylene, and the oily dispersant comprises at least one of glycerol, Triton X-100, polyvinylpyrrolidone and polyethylene glycol.
7. The soft package lithium ion battery of claim 1, wherein the substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer comprises at least one of polyethylene, polypropylene, polyethylene terephthalate and polyimide.
8. The soft-packed lithium ion battery of claim 1, wherein the insulating layer comprises inorganic particles comprising at least one of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, cerium oxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate.
9. The soft-packed lithium ion battery of claim 1, wherein the tie layer comprises at least one of polyvinylidene fluoride, copolymers of vinylidene fluoride-hexafluoropropylene, polyamides, polyacrylonitriles, polyacrylates, polyacrylic acid salts, polyvinylpyrollidones, polyvinyl ethers, polymethyl methacrylates, polytetrafluoroethylene, and polyhexafluoropropylene.
10. The soft package lithium ion battery of claim 1, wherein the insulating layer is disposed on a surface of the substrate layer, and the bonding layer is disposed on the surface of the substrate layer and the insulating layer, respectively.
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