CN109532147A - A kind of lithium battery Soft Roll aluminum plastic film and preparation method thereof for blocking water fire-retardant - Google Patents

A kind of lithium battery Soft Roll aluminum plastic film and preparation method thereof for blocking water fire-retardant Download PDF

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CN109532147A
CN109532147A CN201811370367.7A CN201811370367A CN109532147A CN 109532147 A CN109532147 A CN 109532147A CN 201811370367 A CN201811370367 A CN 201811370367A CN 109532147 A CN109532147 A CN 109532147A
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layer
retardant
lithium battery
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plastic film
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不公告发明人
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Changsha Is As Small As Mdt Infotech Ltd
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    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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    • B32LAYERED PRODUCTS
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
    • 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
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    • H01M50/124Primary casings; Jackets or wrappings characterised by the material having a layered structure
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    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/06Coating on the layer surface on metal layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
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    • B32B2307/3065Flame resistant or retardant, fire resistant or retardant
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    • B32B2307/70Other properties
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Abstract

The invention discloses a kind of lithium battery Soft Roll aluminum plastic films and preparation method thereof for blocking water fire-retardant, belong to the electrically prepared field of lithium.The lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, it is outer to be successively arranged the flame-retardant layer that blocks water, adhesive layer, coextruded layer and wearing layer using aluminium foil layer as middle layer;The flame-retardant layer that blocks water, thermosetting plastic layer, adhesive layer, hot sealing layer are successively arranged in it;The flame-retardant layer that blocks water includes: organic siliconresin, and melamine, melamine phosphate, hexamethoxymethyl melamine resin, be carbonized fento cellulose, lauryl sodium sulfate.The present invention is by using hexamethoxymethyl melamine resin, and be carbonized fento cellulose, and lauryl sodium sulfate is reinforcement system, improves the water preventing ability and anti-flammability of the lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant.

Description

A kind of lithium battery Soft Roll aluminum plastic film and preparation method thereof for blocking water fire-retardant
Technical field
The invention belongs to the electrically prepared fields of lithium, and in particular to a kind of lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant and its system Preparation Method.
Background technique
New Green Energy source battery of the lithium ion battery as a new generation, with light-weight, capacity density is big, voltage is high, nothing The advantages that memory effect, and be widely used in the portable electronic devices such as laptop, mobile phone, digital camera, in recent years Gradually develop to new-energy automobile field.Just because of extensive use of the lithium battery in national life, therefore to the peace of lithium battery Full performance proposes increasingly higher demands.Traditional li battery shell is the punching press for passing through mold with metal materials such as iron, aluminium, copper Splendid attire electrolyte container is made, but due to the rigidity and brittleness of metal material, there are some potential safety problemss.For metal-back Some security risks that the lithium battery of packaging occurs in use, a kind of novel Soft Roll aluminium plastic composite packaging material are met the tendency of And it gives birth to.Aluminum-plastic composite membrane is usually combined by trilaminate material, from outside to inside respectively protective layer, aluminium layer and anti-corrosion layer. In general, outermost effect is to protect aluminium foil not to be scratched, and need with being folded without breaking, rub resistance, shock resistance; The aluminium layer of middle layer is for completely cutting off air and vapor;The anti-corrosion layer of innermost layer will protect aluminium foil not corroded by electrolyte, together When need with cutting resistance because metal burr when vacuumizing on tab may pierce through inner layer material.For lithium from The plastic-aluminum packaging film of sub- battery plays a crucial role the stability and safety of battery.Hexafluoro in lithium battery The fluorine-containing materials such as aluminum phosphate, which meet water, can discharge strong corrosive hydrofluoric acid, can do great damage, seriously affect to the internal layer of aluminium foil The cycle-index and service life of battery accelerate the failure of battery, therefore have to the corrosion resistance of plastic-aluminum film inner layer higher It is required that.The outer layer of aluminum plastic film needs higher crocking resistance, prevents battery abrasion in process and falls and make At battery local defect, therefore how to improve the resistance to corrosion of plastic-aluminum film inner layer and the crocking resistance of outer layer to Guan Chong It wants.
Chinese patent application document " a kind of Soft Roll aluminum plastic film for lithium ion battery and preparation method thereof (publication number: CN106784417A a kind of aluminum plastic film) " is disclosed, including the aluminium foil layer positioned at middle layer, is respectively equipped with inside and outside the aluminium foil layer Diamond alkene-nickel-phosphorous plating layer.The present invention provides a kind of novel for the Soft Roll aluminum plastic film of lithium ion battery and its preparation side Method.The aluminum-plastic composite membrane has cold stamping shaped property good, after being fabricated to soft package lithium battery, has stronger water proof, oxygen barrier, resistance to It punctures, electrolyte resistance corrodes, good flame resistance, the advantages that being not readily separated peeling between layers, with excellent corrosion-resistant and anti- Frictional behaviour, but it is insufficient to there is water preventing ability, anti-flammability.
Summary of the invention
The object of the present invention is to provide a kind of lithium battery Soft Roll aluminum plastic films and preparation method thereof for blocking water fire-retardant, to solve Patent Application Publication " a kind of Soft Roll aluminum plastic film for lithium ion battery and preparation method thereof (publication number: CN106784417A on the basis of coating disclosed in) ", how to optimize component, dosage, method etc., solve water preventing ability, anti-flammability Insufficient problem.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, using aluminium foil layer as middle layer, it is outer be successively arranged block water it is fire-retardant Layer, adhesive layer, coextruded layer and wearing layer;The flame-retardant layer that blocks water, thermosetting plastic layer, adhesive layer, hot sealing layer are successively arranged in it; The flame-retardant layer that blocks water includes: organic siliconresin, melamine, melamine phosphate, hexamethoxymethyl melamine resin, Be carbonized fento cellulose, lauryl sodium sulfate;
The hexamethoxymethyl melamine resin, be carbonized fento cellulose, and the ratio of lauryl sodium sulfate is (20-30): (6-8): (10-20).
Further, the hexamethoxymethyl melamine resin, be carbonized fento cellulose, lauryl sodium sulfate Ratio is 25:7:2.
Further, the flame-retardant layer that blocks water is as unit of parts by weight, including following raw material: organic siliconresin 100-120 Part, it 10-20 parts of melamine, 10-20 parts of melamine phosphate, 20-30 parts of hexamethoxymethyl melamine resin, is carbonized micro- 6-8 parts of fibrillated fibers element, 10-20 parts of lauryl sodium sulfate.
Further, the flame-retardant layer that blocks water is as unit of parts by weight, including following raw material: 110 parts of organic siliconresin, three It 15 parts of poly cyanamid, 15 parts of melamine phosphate, 25 parts of hexamethoxymethyl melamine resin, is carbonized 7 parts of fento cellulose, 2 parts of lauryl sodium sulfate.
Further, the adhesive layer thickness is 10-30 μm;The coextruded layer is that nylon melts to be formed with polyethylene, thick Degree is 10-30 μm;The wearing layer is with a thickness of 5-10 microns;The thermosetting plastic layer is with a thickness of 5-10 μm;The hot sealing layer With a thickness of 10-20 μm.
Further, the aluminium foil layer with a thickness of 80-95 μm, the flame-retardant layer that blocks water with a thickness of 10-20 μm.
Further, the carbonization fento cellulose is the product that fibrillation plant fiber carries out high temperature anaerobic carbonization.
Further, the average diameter of the carbonization fento cellulose is 10-20nm.
Further, the preparation method of the carbonization fento cellulose is to be sent using bleaching hardwood chemical pulp as raw material Fiberizer mashing grinding handles pulp suspension using mill, and swollen pretreatment stage uses between the biggish mill of 0.8-1.0mm Gap treatment process, it is ensured that swelling agent is sufficiently mixed with fiber, and swollen is completed in 5-8min;Gradually adjust disk mill gap extremely later Mashing processing is repeated in 0.1-0.05mm, and amounting to the processing time is 15-30min, completes microfibril separation, above-mentioned microfibril Suspension send high pressure homogenizer, recycles 10-15 times under the conditions of 40-60MPa, after freeze-dried, 80 under the conditions of Ar gas, 120,250 DEG C of gradient increased temperature carbonizations, obtain carbonization fento cellulose.
A kind of preparation method according to the above-mentioned lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, comprising the following steps: (1) It is respectively coated the flame-retardant layer that blocks water in aluminium foil layer two sides, then coated outside one layer of flame-retardant layer that blocks water wherein and solidifies thermosetting property modeling Then glue-line connects hot sealing layer by adhesive layer;(2) it blocks water outside flame-retardant layer at other one layer, coextruded layer and adhesive layer is carried out Be laminated it is compound, squeeze out combined temp be 200 DEG C;(3) wearing layer is evenly applied to co-extrusion layer surface after, then puts aluminium foil It is placed under 60-70 DEG C of environment and dries to get the lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant of the invention.
The invention has the following advantages:
(1) as the data of embodiment 1-3 and comparative example 5 as it can be seen that the lithium battery Soft Roll for blocking water fire-retardant made from embodiment 1-3 With the water preventing ability of aluminum plastic film and anti-flammability be significantly higher than comparative example 5 made from water preventing ability and anti-flammability;Simultaneously by embodiment 1-3's Data are as it can be seen that embodiment 1 is optimum embodiment.
(2) by embodiment 1 and the data of comparative example 1-4 as it can be seen that hexamethoxymethyl melamine resin, be carbonized fento chemical fibre Dimension element, lauryl sodium sulfate are mentioned in the lithium battery Soft Roll that preparation blocks water fire-retardant with synergistic effect, collaboration is played in aluminum plastic film The water preventing ability and anti-flammability of the high lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant;This is:
The present invention is outer to be successively arranged the flame-retardant layer that blocks water, adhesive layer, coextruded layer and wearing layer using aluminium foil layer as middle layer; The flame-retardant layer that blocks water, thermosetting plastic layer, adhesive layer, hot sealing layer are successively arranged in it, the flame-retardant layer that blocks water is with organic siliconresin Based on, a certain amount of melamine is added, melamine phosphate realizes the fire-retardant performance that blocks water as fire retardant.But By comparative example 1 it is found that only adding above-mentioned component can not achieve satisfactory water preventing ability and flame resistance effect, therefore applicant By repetition test, discovery is added to hexamethoxymethyl melamine resin, and be carbonized fento cellulose, lauryl sodium sulfate In the lithium battery Soft Roll that preparation blocks water fire-retardant with playing synergistic effect in aluminum plastic film.
Speculate that its possible mechanism be hexamethoxymethyl melamine resin is water soluble solid agent, can promote organosilicon tree Rouge has good film forming and ductility in aluminium foil surface film-forming, promotes the film forming of organic siliconresin and complete Property, to enhance water preventing ability;The single fiber scale of carbonization fento cellulose is 4nm or so, and the scale of cellulose is 20- 60nm has extremely strong water preventing ability and dispersibility, is not easy to agglomerate, high-specific surface area can be preferably bonded after carbonization Aluminium foil, while being formed a film using its own as skeletal support hexamethoxymethyl melamine resin dispersion, the flame-retardant layer so that enhancing blocks water Waterproofness, its is nonflammable at high temperature, can effectively improve hexamethoxymethyl melamine resin and organic siliconresin Fusing point and burning point, to improve anti-flammability;Lauryl sodium sulfate primarily serves dispersion effect, can be carbonized to inorganic material micro- Fibrillated fibers element carries out surface and is modified, to realize its evenly dispersed hexamethoxymethyl melamine resin and organic siliconresin In, the waterproofness of the sealant of formation is greatly improved, and its burning point that can further increase resin, improves fire-retardant Property.
(3) by the data of comparative example 6-8 as it can be seen that hexamethoxymethyl melamine resin, be carbonized fento cellulose, and 12 The weight ratio of sodium alkyl sulfate is not at (20-30): (6-8): when in (10-20) range, the waterproofness and resistance of aluminum plastic film obtained The numerical value of combustion property numerical value and embodiment 1-3 is very different, much smaller than the numerical value of embodiment 1-3, with the prior art (comparative example 5) Numerical value is suitable.Hexamethoxymethyl melamine resin of the present invention, be carbonized fento cellulose, and lauryl sodium sulfate is as reinforcement System, by addition hexakis-methoxy methyl melamine when embodiment 1-3 control prepares the lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant Polyimide resin, be carbonized fento cellulose, and the weight ratio of lauryl sodium sulfate is (20-30): (6-8): (10-20), realizes The film forming and integrality for promoting organic siliconresin in reinforcement system using hexamethoxymethyl melamine resin, to enhance resistance It is aqueous;The fento cellulose that is carbonized is formed a film using its own as skeletal support hexamethoxymethyl melamine resin dispersion, to increase The waterproofness of the strong flame-retardant layer that blocks water, its is nonflammable at high temperature, to improve anti-flammability;Lauryl sodium sulfate is micro- to being carbonized It is modified that fibrillated fibers carry out surface, thus realize in its evenly dispersed hexamethoxymethyl melamine resin and organic siliconresin, The waterproofness of the sealant of formation is greatly improved, and its burning point that can further increase resin, improves anti-flammability, So that hexamethoxymethyl melamine resin, be carbonized fento cellulose, and the reinforcement system that lauryl sodium sulfate is constituted is at this In the lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant of invention, collaboration improves the resistance for the lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant Aqueous and anti-flammability.
Specific embodiment
To facilitate a better understanding of the present invention, it is illustrated by the following examples, these examples belong to protection of the invention Range, but do not limit the scope of the invention.
In embodiment, a kind of lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, it is outer successively to set using aluminium foil layer as middle layer Block water flame-retardant layer, adhesive layer, coextruded layer and wearing layer;The flame-retardant layer that blocks water, thermosetting plastic layer, bonding are successively arranged in it Layer, hot sealing layer;The flame-retardant layer that blocks water is as unit of parts by weight, including following raw material: 100-120 parts of organic siliconresin, trimerization 10-20 parts of cyanamide, 10-20 parts of melamine phosphate, 20-30 parts of hexamethoxymethyl melamine resin, be carbonized fento chemical fibre 6-8 parts of element of dimension, 10-20 parts of lauryl sodium sulfate.
The adhesive layer thickness is 10-30 μm;The coextruded layer is that nylon melts to be formed with polyethylene, with a thickness of 10-30 μ m;The wearing layer is with a thickness of 5-10 microns;The thermosetting plastic layer is with a thickness of 5-10 μm;The hot sealing layer is with a thickness of 10-20 μm。
The aluminium foil layer with a thickness of 80-95 μm, the flame-retardant layer that blocks water with a thickness of 10-20 μm.
The carbonization fento cellulose is the product that fibrillation plant fiber carries out high temperature anaerobic carbonization, and the carbonization is micro- The average diameter of fibrillated fibers element is 10-20nm.The preparation method of the carbonization fento cellulose is to bleach deciduous Learning slurry is raw material, send fiberizer mashing grinding, handles pulp suspension using mill, swollen pretreatment stage uses 0.8- The biggish disk mill gap treatment process of 1.0mm, it is ensured that swelling agent is sufficiently mixed with fiber, and swollen is completed in 5-8min;Later by To 0.1-0.05mm mashing processing is repeated, amounting to the processing time is 15-30min, completes microfibril in successive step disk mill gap Separation, above-mentioned microfibril suspension send high pressure homogenizer, recycles 10-15 times under the conditions of 40-60MPa, after freeze-dried, 80,120,250 DEG C of gradient increased temperature carbonizations under the conditions of Ar gas, obtain carbonization fento cellulose.
A kind of preparation method according to the above-mentioned lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, comprising the following steps: (1) It is respectively coated the flame-retardant layer that blocks water in aluminium foil layer two sides, then coated outside one layer of flame-retardant layer that blocks water wherein and solidifies thermosetting property modeling Then glue-line connects hot sealing layer by adhesive layer;(2) it blocks water outside flame-retardant layer at other one layer, coextruded layer and adhesive layer is carried out Be laminated it is compound, squeeze out combined temp be 200 DEG C;(3) wearing layer is evenly applied to co-extrusion layer surface after, then puts aluminium foil It is placed under 60-70 DEG C of environment and dries to get the lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant of the invention.
Embodiment 1
A kind of lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, using aluminium foil layer as middle layer, it is outer be successively arranged block water it is fire-retardant Layer, adhesive layer, coextruded layer and wearing layer;The flame-retardant layer that blocks water, thermosetting plastic layer, adhesive layer, hot sealing layer are successively arranged in it; The flame-retardant layer that blocks water is as unit of parts by weight, including following raw material: 110 parts of organic siliconresin, 15 parts of melamine, and melamine It 15 parts of amine phosphate, 25 parts of hexamethoxymethyl melamine resin, is carbonized 7 parts of fento cellulose, lauryl sodium sulfate 2 Part.
The adhesive layer thickness is 20 μm;The coextruded layer is that nylon melts to be formed with polyethylene, with a thickness of 20 μm;It is described Wearing layer is with a thickness of 7.5 microns;The thermosetting plastic layer is with a thickness of 7.5 μm;The hot sealing layer is with a thickness of 15 μm.
The aluminium foil layer with a thickness of 90 μm, the flame-retardant layer that blocks water with a thickness of 15 μm.
The carbonization fibrillation fiber is the product that fibrillation plant fiber carries out high temperature anaerobic carbonization, the carbonization fento The average diameter of chemical fibre dimension is 15nm.
The preparation method of the carbonization fento cellulose is to send fiberizer to be beaten to bleach hardwood chemical pulp as raw material Grinding handles pulp suspension using mill, and swollen pretreatment stage uses the biggish disk mill gap treatment process of 1.0mm, really It protects swelling agent to be sufficiently mixed with fiber, swollen is completed in 7min;Gradually adjustment disk mill gap is repeated to 0.075mm later Mashing processing, amounting to the processing time is 20min, completes microfibril separation, and above-mentioned microfibril suspension send high pressure homogenizer, It is recycled 12 times under the conditions of 50MPa, after freeze-dried, 80,120,250 DEG C of gradient increased temperature carbonizations, obtain carbon under the conditions of Ar gas Change fento cellulose.
A kind of preparation method according to the above-mentioned lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, comprising the following steps: (1) It is respectively coated the flame-retardant layer that blocks water in aluminium foil layer two sides, then coated outside one layer of flame-retardant layer that blocks water wherein and solidifies thermosetting property modeling Then glue-line connects hot sealing layer by adhesive layer;(2) it blocks water outside flame-retardant layer at other one layer, coextruded layer and adhesive layer is carried out Be laminated it is compound, squeeze out combined temp be 200 DEG C;(3) wearing layer is evenly applied to co-extrusion layer surface after, then puts aluminium foil It is placed under 65 DEG C of environment and dries to get the lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant of the invention.
Embodiment 2
A kind of lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, using aluminium foil layer as middle layer, it is outer be successively arranged block water it is fire-retardant Layer, adhesive layer, coextruded layer and wearing layer;The flame-retardant layer that blocks water, thermosetting plastic layer, adhesive layer, hot sealing layer are successively arranged in it; The flame-retardant layer that blocks water is as unit of parts by weight, including following raw material: 100 parts of organic siliconresin, 20 parts of melamine, and melamine It 10 parts of amine phosphate, 30 parts of hexamethoxymethyl melamine resin, is carbonized 6 parts of fento cellulose, lauryl sodium sulfate 20 Part.
The adhesive layer thickness is 10 μm;The coextruded layer is that nylon melts to be formed with polyethylene, with a thickness of 30 μm;It is described Wearing layer is with a thickness of 5 microns;The thermosetting plastic layer is with a thickness of 10 μm;The hot sealing layer is with a thickness of 10 μm.
The aluminium foil layer with a thickness of 95 μm, the flame-retardant layer that blocks water with a thickness of 10 μm.
The carbonization fibrillation fiber is the product that fibrillation plant fiber carries out high temperature anaerobic carbonization, the carbonization
The preparation method of the carbonization fento cellulose is to send fiberizer to be beaten to bleach hardwood chemical pulp as raw material Grinding handles pulp suspension using mill, and swollen pretreatment stage uses the biggish disk mill gap treatment process of 0.8mm, really It protects swelling agent to be sufficiently mixed with fiber, swollen is completed in 8min;Gradually adjustment disk mill gap is repeated and beats to 0.1mm later Slurry processing, amounting to the processing time is 30min, completes microfibril separation, and above-mentioned microfibril suspension send high pressure homogenizer, It is recycled 15 times under the conditions of 40MPa, after freeze-dried, 80,120,250 DEG C of gradient increased temperature carbonizations, obtain carbon under the conditions of Ar gas Change fento cellulose.
A kind of preparation method according to the above-mentioned lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, comprising the following steps: (1) It is respectively coated the flame-retardant layer that blocks water in aluminium foil layer two sides, then coated outside one layer of flame-retardant layer that blocks water wherein and solidifies thermosetting property modeling Then glue-line connects hot sealing layer by adhesive layer;(2) it blocks water outside flame-retardant layer at other one layer, coextruded layer and adhesive layer is carried out Be laminated it is compound, squeeze out combined temp be 200 DEG C;(3) wearing layer is evenly applied to co-extrusion layer surface after, then puts aluminium foil It is placed under 60 DEG C of environment and dries to get the lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant of the invention.
Embodiment 3
A kind of lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, using aluminium foil layer as middle layer, it is outer be successively arranged block water it is fire-retardant Layer, adhesive layer, coextruded layer and wearing layer;The flame-retardant layer that blocks water, thermosetting plastic layer, adhesive layer, hot sealing layer are successively arranged in it; The flame-retardant layer that blocks water is as unit of parts by weight, including following raw material: 120 parts of organic siliconresin, 10 parts of melamine, and melamine It 20 parts of amine phosphate, 20 parts of hexamethoxymethyl melamine resin, is carbonized 8 parts of fento cellulose, lauryl sodium sulfate 10 Part.
The adhesive layer thickness is 30 μm;The coextruded layer is that nylon melts to be formed with polyethylene, with a thickness of 10 μm;It is described Wearing layer is with a thickness of 10 microns;The thermosetting plastic layer is with a thickness of 5 μm;The hot sealing layer is with a thickness of 20 μm.
The aluminium foil layer with a thickness of 80 μm, the flame-retardant layer that blocks water with a thickness of 20 μm.
The carbonization fibrillation fiber is the product that fibrillation plant fiber carries out high temperature anaerobic carbonization, the carbonization
The preparation method of the carbonization fento cellulose is to send fiberizer to be beaten to bleach hardwood chemical pulp as raw material Grinding handles pulp suspension using mill, and swollen pretreatment stage uses the biggish disk mill gap treatment process of 1.0mm, really It protects swelling agent to be sufficiently mixed with fiber, swollen is completed in 5min;Gradually adjustment disk mill gap is repeated and beats to 0.05mm later Slurry processing, amounting to the processing time is 15min, completes microfibril separation, and above-mentioned microfibril suspension send high pressure homogenizer, It is recycled 10 times under the conditions of 60MPa, after freeze-dried, 80,120,250 DEG C of gradient increased temperature carbonizations, obtain carbon under the conditions of Ar gas Change fento cellulose.
A kind of preparation method according to the above-mentioned lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, which is characterized in that including Following steps: (1) being respectively coated the flame-retardant layer that blocks water in aluminium foil layer two sides, then coats simultaneously outside one layer of flame-retardant layer that blocks water wherein Solidify thermosetting plastic layer, hot sealing layer is then connected by adhesive layer;(2) it blocks water outside flame-retardant layer at other one layer, by coextruded layer Be laminated with adhesive layer it is compound, squeeze out combined temp be 200 DEG C;(3) wearing layer is evenly applied to co-extrusion layer surface after, Then aluminium foil is placed under 70 DEG C of environment and is dried to get the lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant of the invention.
Comparative example 1
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that the lithium battery Soft Roll aluminium that preparation blocks water fire-retardant Lack hexamethoxymethyl melamine resin in the raw material of plastic film, be carbonized fento cellulose, lauryl sodium sulfate.
Comparative example 2
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that the lithium battery Soft Roll aluminium that preparation blocks water fire-retardant Lack hexamethoxymethyl melamine resin in the raw material of plastic film.
Comparative example 3
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that the lithium battery Soft Roll aluminium that preparation blocks water fire-retardant Lack carbonization fento cellulose in the raw material of plastic film.
Comparative example 4
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that the lithium battery Soft Roll aluminium that preparation blocks water fire-retardant Lack lauryl sodium sulfate in the raw material of plastic film.
Comparative example 5
Using Chinese patent application document, " a kind of Soft Roll aluminum plastic film for lithium ion battery and preparation method thereof is (open Number: method described in specific embodiment 1 prepares coating in CN106784417A) ".
Comparative example 6
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that the lithium battery Soft Roll aluminium that preparation blocks water fire-retardant 40 parts of hexamethoxymethyl melamine resin in the raw material of plastic film are carbonized 4 parts of fento cellulose, lauryl sodium sulfate 30 Part.
Comparative example 7
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that the lithium battery Soft Roll aluminium that preparation blocks water fire-retardant 15 parts of hexamethoxymethyl melamine resin in the raw material of plastic film are carbonized 10 parts of fento cellulose, lauryl sodium sulfate 30 Part.
Comparative example 8
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that the lithium battery Soft Roll aluminium that preparation blocks water fire-retardant 40 parts of hexamethoxymethyl melamine resin in the raw material of plastic film are carbonized 4 parts of fento cellulose, 5 parts of lauryl sodium sulfate.
To product made from embodiment 1-3 and comparative example 1-8, it is made into 200Ah lithium ion battery respectively, then according to current row The safety of the standard GB/T18287-2013 detection lithium ion battery of industry.According to GB1037 standard, water penetration tester is used Through the permeable amount of the aluminum plastic film of preparation in test for 24 hours, as a result as shown in the table.
As seen from the above table: (1) as the data of embodiment 1-3 and comparative example 5 as it can be seen that blocking water made from embodiment 1-3 fire-retardant Lithium battery Soft Roll aluminum plastic film water preventing ability and anti-flammability be significantly higher than water preventing ability made from comparative example 5 and anti-flammability;Simultaneously By the data of embodiment 1-3 as it can be seen that embodiment 1 is optimum embodiment.
(2) by embodiment 1 and the data of comparative example 1-4 as it can be seen that hexamethoxymethyl melamine resin, be carbonized fento chemical fibre Dimension element, lauryl sodium sulfate are mentioned in the lithium battery Soft Roll that preparation blocks water fire-retardant with synergistic effect, collaboration is played in aluminum plastic film The water preventing ability and anti-flammability of the high lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant;This is:
The present invention is outer to be successively arranged the flame-retardant layer that blocks water, adhesive layer, coextruded layer and wearing layer using aluminium foil layer as middle layer; The flame-retardant layer that blocks water, thermosetting plastic layer, adhesive layer, hot sealing layer are successively arranged in it, the flame-retardant layer that blocks water is with organic siliconresin Based on, a certain amount of melamine is added, melamine phosphate realizes the fire-retardant performance that blocks water as fire retardant.But By comparative example 1 it is found that only adding above-mentioned component can not achieve satisfactory water preventing ability and flame resistance effect, therefore applicant By repetition test, discovery is added to hexamethoxymethyl melamine resin, and be carbonized fento cellulose, lauryl sodium sulfate In the lithium battery Soft Roll that preparation blocks water fire-retardant with playing synergistic effect in aluminum plastic film.
Speculate that its possible mechanism be hexamethoxymethyl melamine resin is water soluble solid agent, can promote organosilicon tree Rouge has good film forming and ductility in aluminium foil surface film-forming, promotes the film forming of organic siliconresin and complete Property, to enhance water preventing ability;The single fiber scale of carbonization fibrillation fiber is 4nm or so, and the scale of cellulose is 20-60nm, After carbonization, there is extremely strong water preventing ability and dispersibility, be not easy to agglomerate, high-specific surface area can preferably be bonded aluminium foil, It is formed a film simultaneously using its own as skeletal support hexamethoxymethyl melamine resin dispersion, the waterproof of flame-retardant layer so that enhancing blocks water Property, its is nonflammable at high temperature, can effectively improve hexamethoxymethyl melamine resin and organic siliconresin fusing point and Burning point, to improve anti-flammability;Lauryl sodium sulfate primarily serves dispersion effect, and can be carbonized to inorganic material fento chemical fibre It is modified that dimension carries out surface, thus realize in its evenly dispersed hexamethoxymethyl melamine resin and organic siliconresin, formation The waterproofness of sealant is greatly improved, and its burning point that can further increase resin, improves anti-flammability.
(3) by the data of comparative example 6-8 as it can be seen that hexamethoxymethyl melamine resin, be carbonized fento cellulose, and 12 The weight ratio of sodium alkyl sulfate is not at (20-30): (6-8): when in (10-20) range, the waterproofness and resistance of aluminum plastic film obtained The numerical value of combustion property numerical value and embodiment 1-3 is very different, much smaller than the numerical value of embodiment 1-3, with the prior art (comparative example 5) Numerical value is suitable.Hexamethoxymethyl melamine resin of the present invention, be carbonized fento cellulose, and lauryl sodium sulfate is as reinforcement System, by addition hexakis-methoxy methyl melamine when embodiment 1-3 control prepares the lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant Polyimide resin, be carbonized fento cellulose, and the weight ratio of lauryl sodium sulfate is (20-30): (6-8): (10-20), realizes The film forming and integrality for promoting organic siliconresin in reinforcement system using hexamethoxymethyl melamine resin, to enhance resistance It is aqueous;The fibrillation fiber that is carbonized is formed a film using its own as skeletal support hexamethoxymethyl melamine resin dispersion, to enhance Block water the waterproofness of flame-retardant layer, its is nonflammable at high temperature, to improve anti-flammability;Lauryl sodium sulfate is to carbonization fento It is modified that chemical fibre dimension carries out surface, to realize in its evenly dispersed hexamethoxymethyl melamine resin and organic siliconresin, shape At the waterproofness of sealant be greatly improved, and its burning point that can further increase resin improves anti-flammability, makes Hexamethoxymethyl melamine resin is obtained, be carbonized fento cellulose, and the reinforcement system that lauryl sodium sulfate is constituted is in this hair In the bright lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, collaboration improves blocking water for the lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant Property and anti-flammability.
The above content is it cannot be assumed that present invention specific implementation is only limited to these instructions, for the technical field of the invention Those of ordinary skill for, under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all answers When being considered as belonging to present invention scope of patent protection determined by the appended claims.

Claims (10)

1. a kind of lithium battery Soft Roll aluminum plastic film for blocking water fire-retardant, which is characterized in that outer to be successively arranged using aluminium foil layer as middle layer Block water flame-retardant layer, adhesive layer, coextruded layer and wearing layer;The flame-retardant layer that blocks water, thermosetting plastic layer, bonding are successively arranged in it Layer, hot sealing layer;The flame-retardant layer that blocks water includes: organic siliconresin, melamine, melamine phosphate, hexakis-methoxy methyl three Cymel, be carbonized fento cellulose, lauryl sodium sulfate;
The hexamethoxymethyl melamine resin, be carbonized fento cellulose, and the ratio of lauryl sodium sulfate is (20- 30): (6-8): (10-20).
2. the lithium battery Soft Roll aluminum plastic film according to claim 1 for blocking water fire-retardant, which is characterized in that the hexakis-methoxy first Base melamine resin, be carbonized fento cellulose, and the ratio of lauryl sodium sulfate is 25:7:2.
3. the lithium battery Soft Roll aluminum plastic film according to claim 1 for blocking water fire-retardant, which is characterized in that it is described block water it is fire-retardant Layer is as unit of parts by weight, including following raw material: 100-120 parts of organic siliconresin, 10-20 parts of melamine, and melamine phosphorus It 10-20 parts of hydrochlorate, 20-30 parts of hexamethoxymethyl melamine resin, is carbonized 6-8 parts of fento cellulose, dodecyl sulphate 10-20 parts of sodium.
4. the lithium battery Soft Roll aluminum plastic film according to claim 1 for blocking water fire-retardant, which is characterized in that it is described block water it is fire-retardant Layer is as unit of parts by weight, including following raw material: 110 parts of organic siliconresin, 15 parts of melamine, and melamine phosphate 15 Part, it 25 parts of hexamethoxymethyl melamine resin, is carbonized 7 parts of fento cellulose, 2 parts of lauryl sodium sulfate.
5. the lithium battery Soft Roll aluminum plastic film according to claim 1 for blocking water fire-retardant, which is characterized in that the bonding thickness Degree is 10-30 μm;The coextruded layer is that nylon melts to be formed with polyethylene, with a thickness of 10-30 μm;The wearing layer is with a thickness of 5- 10 microns;The thermosetting plastic layer is with a thickness of 5-10 μm;The hot sealing layer is with a thickness of 10-20 μm.
6. the lithium battery Soft Roll aluminum plastic film according to claim 1 for blocking water fire-retardant, which is characterized in that the aluminium foil layer With a thickness of 80-95 μm, the flame-retardant layer that blocks water with a thickness of 10-20 μm.
7. the lithium battery Soft Roll aluminum plastic film according to claim 1 for blocking water fire-retardant, which is characterized in that the carbonization fento Cellulose is the product that fibrillation plant fiber carries out high temperature anaerobic carbonization.
8. the lithium battery Soft Roll aluminum plastic film according to claim 1 for blocking water fire-retardant, which is characterized in that the carbonization fento The average diameter of cellulose is 10-20nm.
9. the lithium battery Soft Roll aluminum plastic film according to claim 1 for blocking water fire-retardant, which is characterized in that the carbonization fento The preparation method of cellulose is to send fiberizer mashing grinding to bleach hardwood chemical pulp as raw material, handled and starched using mill Pulp suspension, swollen pretreatment stage use the biggish disk mill gap treatment process of 0.8-1.0mm, it is ensured that swelling agent is filled with fiber Divide mixing, completes swollen in 5-8min;Gradually to 0.1-0.05mm mashing processing is repeated, always in adjustment disk mill gap later The meter processing time is 15-30min, completes microfibril separation, above-mentioned microfibril suspension send high pressure homogenizer, in 40-60MPa item It is recycled 10-15 times under part, after freeze-dried, 80,120,250 DEG C of gradient increased temperature carbonizations, it is micro- to obtain carbonization under the conditions of Ar gas Fibrillated fibers element.
10. a kind of preparation method of -9 described in any item lithium battery Soft Roll aluminum plastic films for blocking water fire-retardant according to claim 1, Characterized by comprising the following steps: (1) is respectively coated the flame-retardant layer that blocks water in aluminium foil layer two sides, then in one layer of resistance wherein Thermosetting plastic layer is coated and solidified outside water flame-retardant layer, hot sealing layer is then connected by adhesive layer;(2) in the other one layer resistance that blocks water It fires outside layer, coextruded layer with adhesive layer be laminated compound, squeezing out combined temp is 200 DEG C;(3) wearing layer is uniformly applied after It is overlying on co-extrusion layer surface, then aluminium foil is placed under 60-70 DEG C of environment and is dried to get the fire-retardant lithium battery that blocks water of the invention Soft Roll aluminum plastic film.
CN201811370367.7A 2018-11-17 2018-11-17 A kind of lithium battery Soft Roll aluminum plastic film and preparation method thereof for blocking water fire-retardant Withdrawn CN109532147A (en)

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CN111540848A (en) * 2020-05-14 2020-08-14 华鼎国联四川动力电池有限公司 Lithium ion battery aluminum plastic film and preparation method thereof
US20210367299A1 (en) * 2020-05-25 2021-11-25 Honda Motor Co., Ltd. Battery cell
JP7482336B1 (en) 2023-09-13 2024-05-13 利昌工業株式会社 Method for producing microfibrillated cellulose body

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CN106784417A (en) * 2016-12-14 2017-05-31 郑州华晶金刚石股份有限公司 A kind of Soft Roll aluminum plastic film for lithium ion battery and preparation method thereof
CN108598552A (en) * 2018-04-04 2018-09-28 徐雄剑 A kind of lithium battery encapsulation composite membrane and preparation method thereof for blocking water fire-retardant

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CN104562823A (en) * 2014-12-11 2015-04-29 天津科技大学 Synchronization method for preparing microfibrillated cellulose and application of microfibrillated cellulose in strengthening of paper
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CN111540848A (en) * 2020-05-14 2020-08-14 华鼎国联四川动力电池有限公司 Lithium ion battery aluminum plastic film and preparation method thereof
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