CN108659772A - Casting glue and battery pack - Google Patents

Casting glue and battery pack Download PDF

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Publication number
CN108659772A
CN108659772A CN201710196558.5A CN201710196558A CN108659772A CN 108659772 A CN108659772 A CN 108659772A CN 201710196558 A CN201710196558 A CN 201710196558A CN 108659772 A CN108659772 A CN 108659772A
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CN
China
Prior art keywords
casting glue
chain extender
isocyanates
glycol
molecular weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710196558.5A
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Chinese (zh)
Inventor
熊辉
J·W·江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fu Neng Technology (ganzhou) Co Ltd
Farasis Energy Ganzhou Co Ltd
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Fu Neng Technology (ganzhou) Co Ltd
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Publication date
Application filed by Fu Neng Technology (ganzhou) Co Ltd filed Critical Fu Neng Technology (ganzhou) Co Ltd
Priority to CN201710196558.5A priority Critical patent/CN108659772A/en
Publication of CN108659772A publication Critical patent/CN108659772A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • C09J175/08Polyurethanes from polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4825Polyethers containing two hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/183Sealing members
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • 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

Abstract

The present invention relates to field of batteries, and in particular, to a kind of casting glue and battery pack.The casting glue contains isocyanates prepolymer, chain extender and polymeric alcohol, wherein the number-average molecular weight of the isocyanates prepolymer is 2,000 4500, and the number-average molecular weight of the polymeric alcohol is 250 3500.Casting glue provided by the invention, can be after embedding enters in battery pack by further chemically reacting and mating reaction, and formation can fix well and the sealing structure of sealed cell group so that gained battery pack is with higher reliability, safety.

Description

Casting glue and battery pack
Technical field
The present invention relates to field of batteries, and in particular, to a kind of casting glue and battery pack.
Background technology
Lithium-ion-power cell has many advantages, such as that high voltage height, energy, small, light weight, operating temperature range are wide, lithium Ion battery group has been widely used in every field, is applied especially to electric automobiles.Lithium-ion-power cell group is by certain The lithium-ion-power cell module of quantity is assembled by series-parallel mode;Lithium-ion-power cell module is by certain again The battery cell of quantity is assembled by series-parallel mode;Battery list in major part lithium-ion-power cell module at present Body is mainly fixed battery using plastic rubber bracket.This fixed form causes to can't be an entirety between battery, makes Relative Vibration is easy tod produce between used time battery, fixed form is unreliable;Plastic rubber bracket hardness itself is high, when use be easy because Vibration causes holder to weigh battery wounded;Lithium-ion-power cell module internal does not completely enclose, and steam is easily accessible power battery mould Battery corrosion or the class of insulation is caused to reduce inside block.
Invention content
The filling can be fixed with the casting glue of sealed cell group and contained well the purpose of the present invention is to provide a kind of The battery pack of sealing.
To achieve the goals above, the present invention provides a kind of casting glue, which contains isocyanates prepolymer, expands Chain agent and polymeric alcohol, wherein the number-average molecular weight of the isocyanates prepolymer is 2000-4500, the number of the polymeric alcohol Average molecular weight is 250-3500.
The present invention also provides the battery packs that embedding has above-mentioned casting glue.
Casting glue provided by the invention, can be after embedding enters in battery pack by further chemically reacting and matching cooperation With formation can be fixed well and the sealing structure of sealed cell group so that gained battery pack has higher reliability, peace Quan Xing.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of casting glue, which contains isocyanates prepolymer, chain extender and polymeric alcohol, In, the number-average molecular weight of the isocyanates prepolymer is 2000-4500, and the number-average molecular weight of the polymeric alcohol is 250- 3500。
According to the present invention, isocyanates prepolymer, chain extender and polymeric alcohol in the casting glue enter battery in embedding After group, by the way that certain condition of cure (such as being stored at room temperature the regular hour) is arranged, enable to isocyanates pre- Polymers, chain extender and polymeric alcohol crosslink solidification and obtain the cured product excellent to the sealing effect of battery pack, and can be more Fixed battery cell does not occur significantly to shake and displacement well.Wherein, each in the casting glue in order to preferably play The mating reaction of a active ingredient, it is preferable that the weight ratio of the isocyanates prepolymer, chain extender and polymeric alcohol is 100: 20-110:1-25, more preferably 100:30-100:1-10, more preferably 100:40-60:2-10.
According to the present invention, as described above, the isocyanates prepolymer has isocyanate-terminated, such as can be Both ends respectively connect such prepolymer of an isocyanate molecule.In general, containing first in the isocyanates prepolymer The structural unit that the structural unit and second comonomer that monomer provides provide, the preferred embodiment of the present invention are that described first is single Body is isocyanates monomer, and the second comonomer is alcohols monomer, polyester polyol or polyether polyol.
Wherein, the isocyanates monomer can be any isocyanates monomer that this field routinely uses, and consider To the application of the stack seal of the present invention, it is preferable that the isocyanates monomer is 2,4- toluene di-isocyanate(TDI)s, 2,6- One in toluene di-isocyanate(TDI), 4,4 '-'-diphenylmethane diisocyanates, hexamethylene diisocyanate and naphthalene diisocyanate Kind is a variety of.
Wherein, the alcohols monomer can be any alcohols monomer that this field routinely uses, it is contemplated that electricity of the invention The application of pond group sealing, it is preferable that the alcohols monomer is ethylene glycol, ethylene oxide, propylene oxide, propylene glycol, butanediol, sweet It is one or more in oil, pentaerythrite and mannitol.
Wherein, the polyester polyol can be this field routinely use any can be used for preparing isocyanates pre-polymerization The polyester polyol of object, it is contemplated that the application of stack seal of the invention, it is preferable that the polyester polyol is polyadipate One kind in glycol ester, polypropylene glycol adipate, polyethylene terephthalate and polypropylene terephthalate Or it is a variety of.
Wherein, the polyether polyol can be this field routinely use any can be used for preparing isocyanates pre-polymerization The polyether polyol of object, it is contemplated that the application of stack seal of the invention, it is preferable that the polyether polyol is poly- second two It is one or more in alcohol, polypropylene glycol and polytetramethylene glycol.
Wherein, the content for the structural unit that the structural unit and second comonomer that first monomer provides provide can be this The content of the isocyanates prepolymer of field routine, there is no particular limitation to this by the present invention.
According to the present invention, the isocyanates prepolymer is the prepolymer of the isocyanide acid blocked with certain molecular weight, I.e. number-average molecular weight is 2000-4500.In order to obtain and the chain extender and the better isocyanic acid of polymeric alcohol fiting effect Esters prepolymer, it is preferable that the number-average molecular weight of the isocyanates prepolymer is 2500-4000.
According to the present invention, the isocyanates prepolymer can be made according to the method for this field routine, or Commercially available product, there is no particular limitation to this by the present invention.
According to the present invention, as described above, the chain extender contributes to the growth of polymer chain, promotes the solidification of embedding The effect of the formation of product.Thus, it is preferable that the chain extender is terminal hydroxy group chain extender, Amino End Group chain extender and hydrazine chain extension It is one or more in agent.
Wherein, the terminal hydroxy group chain extender refers to the chain extender that end has hydroxyl, usually dihydric alcohol, trihydroxylic alcohol etc., It is preferably one or more in ethylene glycol, propylene glycol and butanediol.
Wherein, the Amino End Group chain extender refers to the chain extender that end has amino, usually diamine, tertiary amine etc., It is preferably one or more in ethylenediamine, propane diamine and butanediamine.
Wherein, the hydrazine chain extender refers to the compound for having diamine structure, preferably hydrazine, Dimethylhydrazine and uns-dimethylhydrazine In it is one or more.
In a kind of preferred embodiment of the present invention, the chain extender is ethylene glycol, propylene glycol, ethylenediamine and the third two It is one or more in amine.
In accordance with the present invention it is preferred that the polymeric alcohol is one kind or more in polyethylene glycol, polypropylene glycol and polytetramethylene glycol Kind.
It is particularly preferred that the number-average molecular weight of the polymeric alcohol is 450-2800.
According to the present invention, the polymeric alcohol can be commercially available product, can also be made from the method according to this field routine Product, there is no particular limitation to this by the present invention.
According to the present invention, the casting glue, which can also contain others, can promote described in the casting glue fixes and seal The additive of battery pack, the casting glue containing these additives all should be understood as being included within the scope of the invention.
Wherein, the method for casting glue of the invention in the battery pack embedding may be used the method for this field routine into Row, as long as the battery pack embedding is enabled to have the casting glue.For example, can will be arranged on the battery-pack exterior casing The entrance and exit of casting glue, i.e., be provided with the entrance of casting glue in a side lower part of battery-pack exterior casing, opposite side it is upper Portion is provided with the outlet of casting glue, and casting glue is poured into from entrance in shell, and casting glue is flowed and filled naturally, until reaching The spilling of portion outlet, to the battery pack just casting glue of the present invention in embedding.In order to promote to cure, it is preferable that institute It states after casting glue is heated in embedding to battery pack and stands, the heating is described so that the temperature of casting glue is 30-80 DEG C The time of standing is 0.5-20h.It is final to obtain fixed effect and the excellent battery pack of sealing effect.
Although the present invention does not do any restriction to battery pack, but it is especially preferred that above-mentioned casting glue especially suitable for Sealing as lithium-ion-power cell group.Wherein, the lithium-ion-power cell group includes multiple battery cells, wherein excellent Selection of land, battery cell include pole piece and electrolyte, and the pole piece and electrolyte are sealed in battery case, and the pole piece includes just Pole, cathode and isolation film.
According to the present invention, the usually described anode includes plus plate current-collecting body and the positive material on the plus plate current-collecting body surface The bed of material, the positive electrode material layer contain positive active material, combined conductive agent and binder.
Wherein, excellent in order to obtain higher higher energy density, cycle performance, multiplying power discharging property and high temperature resistance Selection of land, the combined conductive agent contain the gentle phase of carbon black and generate carbon fiber;Wherein, the apparent density of the carbon black is 17-50kg/ m3, specific surface area 800-1000m2/ g, conductivity 105-107S/m, such as it is 20-35kg/m that can meet apparent density3, Specific surface area is 900-950m2/ g, conductivity 106-107S/m.Preferably, the carbon black is Ketjen black.
According to the present invention, in the combined conductive agent, in order to enhance the electric conductivity of the combined conductive agent, the gas phase life It is preferably prepared using chemical catalysis gas phase deposition technology at carbon fiber, specifically, the gas phase generates carbon fiber in 873- Under 1473K, using in transition-metal Fe, Co, Ni one kind or its compound as catalyst, by low-carbon hydrocarbon compound, for example, methane, Acetylene and benzene etc. are cracked and are generated.It is further preferred that the diameter that the gas phase generates carbon fiber can be 140-160nm (examples Such as it is 145-155nm), length can be 5-10 μm (being, for example, 6-8 μm), and stretch modulus can be that 1-10GPa (is, for example, 2- 6GPa), density can be 80-100kg/m3(it is, for example, 85-95kg/m3), coefficient of thermal expansion can be -0.5 × 10-6Extremely -1 × 10-6, thermal conductivity can be 1000-2000Wm-1K-1(it is, for example, 1200-1600Wm-1K-1), conductivity can be 105-107S/m (it is, for example, 106-107S/m)。
According to the present invention, the conventional binder being used in positive electrode in this field may be used in the binder, still In order to provide more multi-cellular structure, to make the anode of lithium ion battery obtain the energy of stronger imbibition ability and Chu Na electrolyte Power, and then the cycle life and energy density of battery are improved, the binder is preferably Kynoar (PVDF), polytetrafluoroethyl-ne At least one of alkene (PTFE), polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC) and polyethylene (PE).
According to the present invention, although positive active material, combined conductive agent and binder in the positive electrode material layer contains Amount can change in wider range, be put as long as the required high higher energy density of the present invention, cycle performance, multiplying power can be made The lithium ion battery of electrical property and high temperature resistance, it is preferable that with the positive active material, the combined conductive agent and On the basis of the total weight of the binder, the content of the positive active material is 85-98 weight %, the combined conductive agent Content is 1-10 weight %, and the content of the binder is 0.1-10 weight %.It is highly preferred that with the positive active material, On the basis of the total weight of the combined conductive agent and the binder, the content of the positive active material is 96-98 weight %, The content of the combined conductive agent is 1-5 weight %, and the content of the binder is 0.1-5 weight %.
According to the present invention, the positive active material is the tertiary cathode active material that this field routinely uses, although institute Above-mentioned chemical formula LiCo can be met with material by stating positive active materialpNiqMn1-p-qO2One in represented any ternary material Kind is a variety of, but considers from on the fiting effect of other active ingredients especially conductive agent of positive electrode material layer, it is preferable that The positive active material is LiCo0.2Ni0.5Mn0.3O2、LiCo0.2Ni0.6Mn0.2O2、LiCo0.1Ni0.8Mn0.1O2With LiCo0.05Ni0.9Mn0.05O2In it is one or more.
According to the present invention, in the combined conductive agent, the carbon black and the gas phase generate carbon fiber can be formed " point ", The conductive network that " line " is combined coordinates under the positive active material, obtains higher electric property.Preferably, the charcoal The weight ratio that black gentle phase generates the content of carbon fiber is 2-5:1-2:1.
To the type of the plus plate current-collecting body, there is no particular limitation in the present invention, can be conventional selection.Specifically, institute It can be the materials such as aluminium, copper or steel to state plus plate current-collecting body.In general, just extremely under the structure of positive plate, i.e., the described just extremely piece Under shape, the plus plate current-collecting body also uses the material of laminated structure, for example, aluminium foil, copper foil or Punching steel strip, preferably aluminium foil. The thickness of the plus plate current-collecting body is not particularly limited, can be suitably adjusted according to required lithium ion battery, Such as the thickness of the plus plate current-collecting body is 10-20 μm, preferably 14-18 μm.
It in view of cost and improves under energy density, cycle performance and multiplying power discharging property, it is preferable that the anode collection The thickness of body and positive electrode material layer ratio is 1:5-10.Meeting under this condition, it is preferable that the thickness of the positive electrode material layer is 100-200 μm, preferably 120-180 μm, more preferably 150-160 μm.
According to the present invention, the amount of the positive electrode formed on the plus plate current-collecting body can be 46-50mg/cm2, in this way Lithium ion battery can be made to obtain higher energy density.
According to the present invention, in general, the cathode includes negative current collector and the cathode material being formed on negative current collector Material, the negative material includes negative electrode active material, conductive agent and binder.
Wherein, the negative electrode active material can be the negative electrode active material of this field routine being embedded in and deviate from lithium, Such as one kind in graphite, artificial graphite, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, tin alloy, silicon alloy Or several, preferably graphite, for example, natural graphite.
Wherein, the type and content of the negative electrode binder can be this field conventional selection, such as fluorine resin and Polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) (PTFE), butadiene-styrene rubber (SBR) and carboxymethyl cellulose (CMC) one or more in, preferably butadiene-styrene rubber (SBR) and/or carboxymethyl cellulose (CMC).
Wherein, the cathode conductive agent can be the conductive agent of this field routine, such as carbon black, acetylene black, furnace black, carbon fiber It is one or more in dimension, graphene, carbon nanotube, conductive black and electrically conductive graphite, preferably carbon black and carbon fiber, further The preferably gentle phase of carbon black generates carbon fiber.
According to the present invention, with the negative electrode active material, the total weight of the cathode conductive agent and the negative electrode binder On the basis of, the content of the negative electrode active material is 82-96 weight %, and the content of the cathode conductive agent is 3-8 weight %, institute The content for stating negative electrode binder is 0.1-10 weight %.
According to the present invention, the collector of the cathode can be common negative current collector, such as punching press in lithium ion battery Metal, metal foil, net metal and foamed metal, preferably copper foil.
Wherein, conventional preparation method may be used in the preparation method of the cathode.For example, by negative electrode active material, bearing Pole conductive agent and negative electrode binder are mixed and made into negative electrode slurry with solvent, are coated on the negative current collector, are then done Dry, calendering and cutting can be obtained the cathode.Wherein, method and condition that is dry, rolling and cut can be this field Conventional selection.
According to the present invention, the usual electrolyte contains lithium salts and nonaqueous solvents.The lithium salts can be lithium hexafluoro phosphate, Hexafluoroarsenate lithium, lithium perchlorate, trifluoromethyl sulfonic acid lithium, perfluoro butyl Sulfonic Lithium, lithium aluminate, chlorine lithium aluminate, fluoro sulphonyl are sub- It is one or more in amine lithium, lithium chloride and lithium iodide, most preferably lithium hexafluoro phosphate (LiPF6)。
Wherein, the nonaqueous solvents can be ethylene carbonate (EC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), gamma-butyrolacton, acid anhydrides, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N- methyl vinyls Amine, acetonitrile, N,N-dimethylformamide, sulfolane, dimethyl sulfoxide, dimethyl sulfite and other fluorine-containing, sulfur-bearings contain not It is one or more in the cyclic annular organic ester of saturated bond, the most preferably combination of EC, EMC and DEC, it is further preferred that EC, The volume ratio of EMC and DEC is 1-3:1:4-6.The dosage of the nonaqueous solvents can change in wider range, for example, general feelings Under condition, the dosage of the nonaqueous solvents makes a concentration of 0.1-2mol/L of lithium salts.
Under preferable case, electrolysis additive is also contained in the electrolyte, the electrolysis additive can be fluoro Ethylene carbonate (FEC), propylene sulfite (PS), difluorine oxalic acid boracic acid lithium (LiODFB) and dioxalic acid lithium borate (LiBOB) It is one or more in, preferably fluorinated ethylene carbonate (FEC), propylene sulfite (PS), difluorine oxalic acid boracic acid lithium (LiODFB) and the combination of dioxalic acid lithium borate (LiBOB), it is further preferred that on the basis of the total weight of the electrolyte, The content of the fluorinated ethylene carbonate FEC is 0.1-5 weight %, the content of the propylene sulfite PS is 0.1-5 weights Measure %, the difluorine oxalic acid boracic acid lithium LiODFB content be 0.1-5 weight %, the dioxalic acid lithium borate LiBOB's contains Amount is 0.1-5 weight %.
According to the present invention, the preparation method of lithium ion battery of the invention can be well known for the person skilled in the art Method, in general, this method include that anode, isolation film, cathode are stacked assembling according to top-down lamination pattern, then By anode and aluminium pole ears welding, cathode and copper nickel plating tab welding, aluminum plastic film heat-sealing is carried out later, injection electrolyte, is vacuumized Encapsulation be made battery core, it is infiltrated, chemical conversion and vacuumize to obtain lithium ion battery again.
The infiltration condition includes:Infiltrating time is 20-40h.
The chemical conversion condition includes:Formation voltage is 2.75-4.4V.
The present invention will be described in detail by way of examples below.
Preparation example 1
By dewatered PEG2000 (molecular weight 2000 is purchased from Jiangsu Hai'an Petrochemical Plant) and 4,4 '-hexichol first Alkane diisocyanate (molar ratio 1:2) it is mixed, and is reacted at 80 DEG C, be considered as reaction until NCO% is constant and terminate (about 2h), to which the isocyanates prepolymer P1 that both ends are isocyanide acid blocked be made, number-average molecular weight is about 2500.
Preparation example comparative example 1
According to the method described in preparation example 1, the difference is that, use the PEG200 that molecular weight is 200 (to be purchased from Jiangsu Province Hai'an Petrochemical plant) PEG1000 is replaced, to which the isocyanates prepolymer DP1 that both ends are isocyanide acid blocked, the equal molecule of number be made Amount about 700.
Preparation example comparative example 2
According to the method described in preparation example 1, the difference is that, use the PEG6000 that molecular weight is 6000 (purchased from Jiangsu Province sea Pacify petrochemical plant) PEG1000 is replaced, to which the isocyanates prepolymer DP2 that both ends are isocyanide acid blocked be made, number is divided equally Son amount about 6500.
Casting glue embodiment
The present embodiment is used to illustrate the casting glue of the present invention.
It is prepared according to composition shown in table 1 and obtains the DG1-DG5 of the required casting glue G1-G4 and comparison of the present invention.
Table 1
Note:" isocyanic acid " refers to isocyanates prepolymer, produced as described above.
Battery pack preparation example
The preparation of battery cell includes:
(1) preparation of positive plate
By the LiCo of 940g0.2Ni0.6Mn0.2O2, 25g Kynoar PVDF, 25g Ketjen black ECP and 5g gas phases generate carbon Fiber VCGF is mixed and is scattered under the rotating speed of 3000rpm in 600mL N-methyl pyrrolidones NMP, is stirred 4h, is obtained solid Content is the positive electrode of 50 weight %.Uniform, positive electrode coated weight is smeared in the two-sided dressing on the aluminium foil that thickness is 16 μm For 47mg/cm2.Dried at 90 DEG C, roll, cut into positive plate, positive plate size be 212mm (length) × 156mm (width) × 130 μm (thickness), compacted density 3.12g/cm3, cell positive material coated weight is 40mg/cm2
(2) preparation of negative plate
By 945g graphite (being purchased from Shanghai Shan Shan companies FSN-1 models), 15g conductive agents (commercially available from Timcal companies Super-p Li models), 23g styrene butadiene rubber sbrs (be purchased from A&L companies of Japan, SN-307 models) and 17g sodium carboxymethylcelluloses CMC is uniformly mixed in deionized water, obtains the negative material that solid content is 50 weight %.On the copper foil that thickness is 8 μm Two-sided dressing is smeared uniform.It dries, rolls at 90 DEG C, cut into negative plate, negative plate size is 213mm (length) × 157mm (width) × 127 μm (thickness), compacted density 1.6g/cm3
(2) assembling of battery
By in each embodiment positive plate and polyethylene separators (being purchased from Celgard companies H2013 models) and above-mentioned bear Pole piece stacks assembling according to top-down lamination pattern, then welds anode and aluminium pole ears welding, cathode and copper nickel plating lug It connects, carries out aluminum plastic film heat-sealing later.Then by LiPF6It is dissolved in 100g ethylene carbonates EC, carbonic acid first by the concentration of 1mol/L Ethyl ester EMC and diethyl carbonate DEC (volume ratio EC:EMC:DEC=2:1:5) in the mixed solvent, is then added 2g thereto Fluorinated ethylene carbonate FEC, 2g propylene sulfite PS, 1g difluorine oxalic acid boracic acid lithium LiODFB and 0.5g dioxalic acid lithium borate LiBOB electrolysis additives, to obtain electrolyte.By obtained electrolyte in the amount injection battery case of 2.1g/Ah, to take out true Sky sealing, infiltrated 30h are melted under 3.5V voltages, vacuumize lithium-ion battery monomer is made again.
The preparation of battery case:The metal shell (thickness 2mm) that metallic aluminium is prepared into;The metal shell is removed Oil, derusting then carry out anodized (in the sulfuric acid solution of 20g/L, voltage is to handle 10min under 20V), take out And the dry 20min at 80 DEG C, form antioxidation coating in metal housing surface (thickness is 20 μm);By epoxy powder (purchase From the 3M521+ trades mark of 3M companies, dioxide-containing silica is about 35 weight %, and the content of epoxy resin is about 60 weight %) it uses Static plastic spraying machine is sprayed onto on metal housing surface to form the coating after 0.6mm, and the electrostatic potential of the electrostatic spraying is 35kV; Shell after electrostatic spraying is sent into curing oven, 20min is kept the temperature at 180 DEG C, to obtain battery case, is gathered on the shell The thickness of compound film is 0.5mm.It is arranged with casting glue inlet port, in opposite side face in the lower part of the width profile of battery case Top be arranged casting glue overfall;
100 battery cells are connected in series and are configured in above-mentioned battery case, battery modules are obtained;By casting glue G1 is sent into from the casting glue inlet port of battery case, is stopped when casting glue overfall overflows casting glue, to complete embedding, and After standing 8h, battery pack C1 is obtained;
In the same way, unlike, casting glue G2-G4 and DG1-DG5 is respectively adopted and replaces casting glue G1, to The battery pack C2-C4 and DC1-DC5 of sealing is made.
To the leakproofness of the battery pack of above-mentioned sealing, insulation impedance, stationarity, reliability, tensile strength, tearing strength, Shore hardness and low-temperature bending are tested, and test result is as follows shown in table 2, wherein:
Leakproofness is measured by IP67 waterproof tests;
Finished battery group Insulation test be by battery pack finished product using direct current 1000V test it is total just with shell insulation resistance, Total negative and shell insulation resistance.
Stationarity and reliability are according to GBT 31467.3-2015 lithium ion power storage battery packets for electric vehicle and are System third portion:What security requirement was measured with test method;
Tensile strength is measured according to GB/T 528-2009;
Tearing strength is measured according to GB/T 529-1999;
Shore hardness is measured according to GB/T 531.1-2008;
Low-temperature bending is measured according to GB/T 16777-1997.
Table 2
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (10)

1. a kind of casting glue, which is characterized in that the casting glue contains isocyanates prepolymer, chain extender and polymeric alcohol, wherein The number-average molecular weight of the isocyanates prepolymer is 2000-4500, and the number-average molecular weight of the polymeric alcohol is 250-3500.
2. casting glue according to claim 1, wherein the isocyanates prepolymer, chain extender and polymeric alcohol weight Amount is than being 100:20-110:1-25, preferably 100:30-100:1-10.
3. casting glue according to claim 1 or 2, wherein the number-average molecular weight of the isocyanates prepolymer is The number-average molecular weight of 2500-4000, the polymeric alcohol are 450-2800.
4. according to the casting glue described in any one of claim 1-3, wherein contain in the isocyanates prepolymer The structural unit that the structural unit and second comonomer that one monomer provides provide, wherein first monomer is isocyanates list Body, the second comonomer are alcohols monomer, polyester polyol or polyether polyol.
5. casting glue according to claim 4, wherein the isocyanates monomer be 2,4- toluene di-isocyanate(TDI)s, In 2,6- toluene di-isocyanate(TDI)s, 4,4 '-'-diphenylmethane diisocyanates, hexamethylene diisocyanate and naphthalene diisocyanate It is one or more.
6. casting glue according to claim 4 or 5, wherein the alcohols monomer is ethylene glycol, ethylene oxide, epoxy third It is one or more in alkane, propylene glycol, butanediol, glycerine, pentaerythrite and mannitol;
The polyester polyol be polyethylene glycol adipate, polypropylene glycol adipate, polyethylene terephthalate and It is one or more in polypropylene terephthalate;
The polyether polyol is one or more in polyethylene glycol, polypropylene glycol and polytetramethylene glycol.
7. according to the casting glue described in any one of claim 1-6, wherein the chain extender is terminal hydroxy group chain extender, end It is one or more in amino chain extender and hydrazine chain extender.
8. casting glue according to claim 7, wherein the terminal hydroxy group chain extender is ethylene glycol, propylene glycol and butanediol In it is one or more;
Preferably, the Amino End Group chain extender is one or more in ethylenediamine, propane diamine and butanediamine;
Preferably, the hydrazine chain extender is one or more in hydrazine, Dimethylhydrazine and uns-dimethylhydrazine.
9. according to the casting glue described in any one of claim 1-8, wherein the polymeric alcohol is polyethylene glycol, poly- the third two It is one or more in alcohol and polytetramethylene glycol.
The battery pack of casting glue 10. embedding is had the right described in any one of requirement 1-9.
CN201710196558.5A 2017-03-29 2017-03-29 Casting glue and battery pack Pending CN108659772A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113861381A (en) * 2021-10-13 2021-12-31 东莞市宏达聚氨酯有限公司 Polyurethane pouring sealant and preparation method thereof
WO2022134900A1 (en) * 2020-12-24 2022-06-30 清华大学深圳国际研究生院 Freely cuttable electrochromic device and application

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CN102942894A (en) * 2012-11-29 2013-02-27 宜兴市江南药用化工厂 Double-component low-hardness flame-retardant polyurethane potting adhesive and preparation method thereof
CN105885767A (en) * 2016-06-24 2016-08-24 绵阳惠利电子材料有限公司 MDI-base polyurethane electronic pouring sealant as well as preparation method and application method thereof

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Publication number Priority date Publication date Assignee Title
CN102174171A (en) * 2011-01-12 2011-09-07 厦门誉匠复合材料有限公司 Bubble-free yellowing resistant polyurethane electronic potting adhesive composition and preparation method thereof
CN102942894A (en) * 2012-11-29 2013-02-27 宜兴市江南药用化工厂 Double-component low-hardness flame-retardant polyurethane potting adhesive and preparation method thereof
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