CN113832776A - Highland barley paper for lithium battery packaging and preparation method thereof - Google Patents

Highland barley paper for lithium battery packaging and preparation method thereof Download PDF

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Publication number
CN113832776A
CN113832776A CN202110930169.7A CN202110930169A CN113832776A CN 113832776 A CN113832776 A CN 113832776A CN 202110930169 A CN202110930169 A CN 202110930169A CN 113832776 A CN113832776 A CN 113832776A
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Prior art keywords
highland barley
barley paper
modified filler
composite modified
weight
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Inventor
王自强
王晟
余小龙
杨子文
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Jiangsu Jinyuan New Energy Technology Co ltd
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Jiangsu Jinyuan New Energy Technology Co ltd
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Priority to CN202110930169.7A priority Critical patent/CN113832776A/en
Publication of CN113832776A publication Critical patent/CN113832776A/en
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/52—Epoxy resins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D21H27/38—Multi-ply at least one of the sheets having a fibrous composition differing from that of other sheets

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Cell Separators (AREA)

Abstract

The invention discloses highland barley paper for lithium battery packaging and a preparation method thereof, and particularly relates to the technical field of highland barley paper, which comprises the following steps: wood fiber, cotton fiber, polytetrafluoroethylene, epoxy resin, composite modified filler A, composite modified filler B and organic solvent. The invention can effectively improve the high and low temperature resistance of the highland barley paper, and can ensure the waterproof performance of the highland barley paper after the highland barley paper is rapidly switched under the high and low temperature environment; wood fiber, cotton fiber and polytetrafluoroethylene in the formula are used as main materials of the highland barley paper base material, and the composite fiber b and the composite fiber d are compounded into the highland barley paper base material; electrostatic spinning to prepare silicon dioxide aerogel and waterborne polyurethane resin composite fiber to prepare an intermediate protective film; the nano titanium dioxide and nano silicon dioxide sol composite fiber is prepared by electrostatic spinning, and an outer protective film is prepared, so that the temperature change resistance, the waterproof performance and the flame retardant performance of the highland barley paper can be further enhanced.

Description

Highland barley paper for lithium battery packaging and preparation method thereof
Technical Field
The invention relates to the technical field of highland barley paper, in particular to highland barley paper for lithium battery packaging and a preparation method thereof.
Background
The highland barley paper is named as green shell paper, is commonly known as a cyan thin electric insulation paper board, is prepared by wood fiber or mixed pulp mixed with cotton fiber and through a certain process. Lithium batteries can be broadly classified into two types: lithium metal batteries and lithium ion batteries; the lithium metal battery refers to a battery which uses manganese dioxide as a positive electrode material, uses metal lithium or alloy metal thereof as a negative electrode material and adopts non-aqueous electrolyte solution; the lithium ion battery refers to a battery using a lithium alloy metal oxide as a positive electrode material and graphite as a negative electrode material, and using a non-aqueous electrolyte. The highland barley paper can be pasted on the outside of the cylindrical battery anode, so that the lithium battery anode has good insulation, wear resistance, water resistance and other characteristics, and the short circuit of the anode and the cathode when the lithium battery pack vibrates can be effectively prevented.
The existing highland barley paper for lithium battery packaging has poor high-low temperature resistance, is easy to cause performance damage after the highland barley paper is rapidly switched under high-low temperature environment, and has sharply reduced waterproof performance.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides highland barley paper for lithium battery packaging and a preparation method thereof.
The highland barley paper for lithium battery packaging comprises the following components in percentage by weight: 11.40-12.80% of wood fiber, 8.30-8.90% of cotton fiber, 20.30-20.70% of polytetrafluoroethylene, 22.40-23.80% of epoxy resin, 5.20-5.60% of composite modified filler A, 14.40-15.20% of composite modified filler B and the balance of organic solvent.
Further, the composite modified filler A comprises the following components in percentage by weight: 35.40-36.20% of silicon dioxide aerogel, 0.80-0.90% of defoaming agent and the balance of waterborne polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 34.20-36.40% of nano titanium dioxide, and the balance of nano silicon dioxide sol.
Further, the paint comprises the following components in percentage by weight: 11.40% of wood fiber, 8.30% of cotton fiber, 20.30% of polytetrafluoroethylene, 22.40% of epoxy resin, 5.20% of composite modified filler A, 14.40% of composite modified filler B and 18.00% of organic solvent; the composite modified filler A comprises the following components in percentage by weight: 35.40% of silicon dioxide aerogel, 0.80% of defoaming agent and 63.80% of waterborne polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 34.20 percent of nano titanium dioxide and 65.80 percent of nano silicon dioxide sol.
Further, the paint comprises the following components in percentage by weight: 12.80% of wood fiber, 8.90% of cotton fiber, 20.70% of polytetrafluoroethylene, 23.80% of epoxy resin, 5.60% of composite modified filler A, 15.20% of composite modified filler B and 13.00% of organic solvent; the composite modified filler A comprises the following components in percentage by weight: 36.20% of silicon dioxide aerogel, 0.90% of defoaming agent and 62.90% of waterborne polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 36.40% of nano titanium dioxide and 63.60% of nano silica sol.
Further, the paint comprises the following components in percentage by weight: 12.10% of wood fiber, 8.60% of cotton fiber, 20.50% of polytetrafluoroethylene, 23.10% of epoxy resin, 5.40% of composite modified filler A, 14.80% of composite modified filler B and 15.50% of organic solvent; the composite modified filler A comprises the following components in percentage by weight: 35.80% of silicon dioxide aerogel, 0.85% of defoaming agent and 63.35% of aqueous polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 35.30 percent of nano titanium dioxide and 64.70 percent of nano silicon dioxide sol.
Further, the organic solvent is one or two of butyl acetate, isobutyl acetate, n-propanol and tert-butanol.
The invention also provides a preparation method of the highland barley paper for lithium battery packaging, which comprises the following specific preparation steps:
the method comprises the following steps: weighing the wood fiber, the cotton fiber, the polytetrafluoroethylene, the epoxy resin, the composite modified filler A, the composite modified filler B and the organic solvent in parts by weight;
step two: pulping the wood fibers and the cotton fibers in the step one to obtain pulp;
step three: stirring and mixing the composite modified filler A in the step one and one eighth of the organic solvent by weight, and carrying out ultrasonic treatment for 10-20 minutes to obtain a mixture a;
step four: carrying out electrostatic spinning treatment on the mixture a prepared in the third step to obtain composite fibers b;
step five: stirring and mixing the composite modified filler B in the step one and one fifth of the organic solvent by weight, and carrying out ultrasonic treatment for 15-25 minutes to obtain a mixture c;
step six: performing electrostatic spinning treatment on the mixture c prepared in the fifth step to obtain composite fibers d;
step seven: adding the polytetrafluoroethylene in the step one, a half of the organic solvent in parts by weight, a third of the composite fiber b prepared in the step four and a third of the composite fiber d prepared in the step six into the slurry prepared in the step two together, and carrying out ultrasonic treatment for 20-30 minutes to obtain a mixture e;
step eight: mixing one third of the epoxy resin, one tenth of the organic solvent and the composite fiber b prepared in the fourth step in the first step, and performing ultrasonic treatment for 20-30 minutes to obtain a mixture f;
step nine: mixing two thirds of the epoxy resin, the rest of the organic solvent and the rest of the composite fiber d prepared in the sixth step in parts by weight in the first step, and performing ultrasonic treatment for 20-30 minutes to obtain a mixture g;
step ten: processing the mixture e prepared in the step seven by using a double-screw extruder to prepare a highland barley paper base material, and respectively processing the mixture f prepared in the step eight by using a film blowing machine to prepare an intermediate protective film; respectively processing the mixture g prepared in the ninth step by using a film blowing machine to prepare an outer protective film;
step eleven: performing film coating processing on the outside of the highland barley paper base material: and (3) coating the middle protective films on two sides of the outside of the highland barley paper base material, and coating the outer protective films on the outer sides of the middle protective films to prepare the highland barley paper for lithium battery packaging.
Furthermore, in the third step, the ultrasonic frequency is 1.4-1.8 MHz, and the ultrasonic power is 300-500W; in the fourth step, in the electrostatic spinning process, 12-14 KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 8-10 cm, and the flow speed of the spinning solution is 1.1-1.5 ml/h; in the fifth step, the ultrasonic frequency is 1.7-1.9 MHz, and the ultrasonic power is 300-400W; in the sixth step, in the electrostatic spinning process, 12-14 KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 10-12 cm, and the flow rate of the spinning solution is 1.2-1.8 ml/h; in the seventh step, the eighth step and the ninth step, the ultrasonic frequency is 1.7-1.9 MHz, and the ultrasonic power is 300-400W.
Furthermore, in the third step, the ultrasonic frequency is 1.4MHz, and the ultrasonic power is 300W; in the fourth step, 12KV high voltage is applied in the electrostatic spinning process, the distance between a capillary nozzle of the injector and a grounded receiving device is 8cm, and the flow rate of the spinning solution is 1.1 ml/h; in the fifth step, the ultrasonic frequency is 1.7MHz, and the ultrasonic power is 300W; in the sixth step, in the electrostatic spinning process, 12KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 10cm, and the flow rate of the spinning solution is 1.2 ml/h; in the seventh step, the eighth step and the ninth step, the ultrasonic frequency is 1.7MHz, and the ultrasonic power is 300W.
Furthermore, in the third step, the ultrasonic frequency is 1.6MHz, and the ultrasonic power is 400W; in the fourth step, in the electrostatic spinning process, 13KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 9cm, and the flow rate of the spinning solution is 1.3 ml/h; in the fifth step, the ultrasonic frequency is 1.8MHz, and the ultrasonic power is 350W; in the sixth step, in the electrostatic spinning process, 13KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 11cm, and the flow rate of the spinning solution is 1.5 ml/h; in the seventh step, the eighth step and the ninth step, the ultrasonic frequency is 1.8MHz, and the ultrasonic power is 350W.
The invention has the technical effects and advantages that:
1. the highland barley paper for lithium battery packaging, which is prepared by adopting the raw material formula, can effectively improve the high and low temperature resistance of the highland barley paper, and can ensure the waterproof performance of the highland barley paper after the highland barley paper is rapidly switched under the high and low temperature environment; the wood fiber, the cotton fiber and the polytetrafluoroethylene in the formula are used as main materials of the highland barley paper base material, and the composite fiber b and the composite fiber d are compounded into the highland barley paper base material, so that the temperature change resistance, the flame retardant property and the waterproof property of the highland barley paper base material can be effectively enhanced; blending and compounding the silica aerogel and the waterborne polyurethane resin in the composite modified filler A, then blending the silica aerogel and the waterborne polyurethane resin with an organic solvent and then performing electrostatic spinning to prepare silica aerogel and waterborne polyurethane resin composite fibers, mixing the composite fibers b with epoxy resin and the organic solvent to prepare an intermediate protective film, and covering the highland barley paper with the intermediate protective film; the nano titanium dioxide and the nano silicon dioxide sol in the composite modified filler B are blended and compounded, then are blended with an organic solvent and then are subjected to electrostatic spinning to prepare nano titanium dioxide and nano silicon dioxide sol composite fibers, the composite fibers d are mixed with epoxy resin and the organic solvent to prepare an outer protective film, and the outer protective film is coated outside the middle protective film, so that the temperature change resistance, the waterproof performance and the flame retardant performance of the highland barley paper can be further enhanced;
2. in the process of preparing the highland barley paper for lithium battery packaging, in the third step, the composite modified filler A and the organic solvent are mixed for 1.6MHz ultrasonic treatment, so that the stability and the structural uniformity of the composite fiber b are ensured; in the fourth step, the mixture a is subjected to electrostatic spinning treatment, so that the rapid compounding of the silicon dioxide aerogel and the waterborne polyurethane resin is ensured; in the fifth step, the composite modified filler B and the organic solvent are mixed for 1.8MHz ultrasonic treatment, so that the stability and the structural uniformity of the composite fiber d are ensured; in the sixth step, the mixture c is subjected to electrostatic spinning treatment, so that the rapid compounding of the nano titanium dioxide and the nano silicon dioxide sol is ensured; in the seventh step, the sizing agent, the polytetrafluoroethylene, the organic solvent, the composite fiber b and the composite fiber d are blended, and the composite fiber b and the composite fiber d are added into the highland barley paper base material, so that the temperature change resistance, the waterproof performance and the flame retardant performance of the highland barley paper base material can be effectively enhanced; in the tenth step, the composite fiber b is used as a main raw material to prepare an intermediate protective film, and the composite fiber d is used as a main raw material to prepare an outer protective film; eleventh, the highland barley paper with the five-layer structure is prepared, and the temperature change resistance, the waterproof performance and the flame retardant performance of the highland barley paper can be further enhanced.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides highland barley paper for lithium battery packaging, which comprises the following components in percentage by weight: 11.40% of wood fiber, 8.30% of cotton fiber, 20.30% of polytetrafluoroethylene, 22.40% of epoxy resin, 5.20% of composite modified filler A, 14.40% of composite modified filler B and 18.00% of organic solvent; the composite modified filler A comprises the following components in percentage by weight: 35.40% of silicon dioxide aerogel, 0.80% of defoaming agent and 63.80% of waterborne polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 34.20 percent of nano titanium dioxide and 65.80 percent of nano silicon dioxide sol;
the organic solvent is one or two of butyl acetate, isobutyl acetate, n-propanol and tert-butanol;
the invention also provides a preparation method of the highland barley paper for lithium battery packaging, which comprises the following specific preparation steps:
the method comprises the following steps: weighing the wood fiber, the cotton fiber, the polytetrafluoroethylene, the epoxy resin, the composite modified filler A, the composite modified filler B and the organic solvent in parts by weight;
step two: pulping the wood fibers and the cotton fibers in the step one to obtain pulp;
step three: stirring and mixing the composite modified filler A in the step one and one eighth of the organic solvent by weight, and carrying out ultrasonic treatment for 10 minutes to obtain a mixture a;
step four: carrying out electrostatic spinning treatment on the mixture a prepared in the third step to obtain composite fibers b;
step five: stirring and mixing the composite modified filler B in the step one and one fifth of the organic solvent by weight, and carrying out ultrasonic treatment for 15 minutes at the same time to obtain a mixture c;
step six: performing electrostatic spinning treatment on the mixture c prepared in the fifth step to obtain composite fibers d;
step seven: adding the polytetrafluoroethylene in the step one, one-half of the organic solvent in parts by weight, one-third of the composite fiber b prepared in the step four and one-third of the composite fiber d prepared in the step six into the slurry prepared in the step two together, and carrying out ultrasonic treatment for 20 minutes to obtain a mixture e;
step eight: mixing one third of the epoxy resin in the first step, one tenth of the organic solvent in the first step and the composite fiber b prepared in the fourth step, and performing ultrasonic treatment for 20 minutes to obtain a mixture f;
step nine: mixing two thirds of the epoxy resin, the rest of the organic solvent and the rest of the composite fiber d prepared in the sixth step in parts by weight in the first step, and performing ultrasonic treatment for 20 minutes to obtain a mixture g;
step ten: processing the mixture e prepared in the step seven by using a double-screw extruder to prepare a highland barley paper base material, and respectively processing the mixture f prepared in the step eight by using a film blowing machine to prepare an intermediate protective film; respectively processing the mixture g prepared in the ninth step by using a film blowing machine to prepare an outer protective film;
step eleven: performing film coating processing on the outside of the highland barley paper base material: and (3) coating the middle protective films on two sides of the outside of the highland barley paper base material, and coating the outer protective films on the outer sides of the middle protective films to prepare the highland barley paper for lithium battery packaging.
In the third step, the ultrasonic frequency is 1.4MHz, and the ultrasonic power is 300W; in the fourth step, 12KV high voltage is applied in the electrostatic spinning process, the distance between a capillary nozzle of the injector and a grounded receiving device is 8cm, and the flow rate of the spinning solution is 1.1 ml/h; in the fifth step, the ultrasonic frequency is 1.7MHz, and the ultrasonic power is 300W; in the sixth step, in the electrostatic spinning process, 12KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 10cm, and the flow rate of the spinning solution is 1.2 ml/h; in the seventh step, the eighth step and the ninth step, the ultrasonic frequency is 1.7MHz, and the ultrasonic power is 300W.
Example 2:
different from the embodiment 1, the material comprises the following components in percentage by weight: 12.80% of wood fiber, 8.90% of cotton fiber, 20.70% of polytetrafluoroethylene, 23.80% of epoxy resin, 5.60% of composite modified filler A, 15.20% of composite modified filler B and 13.00% of organic solvent; the composite modified filler A comprises the following components in percentage by weight: 36.20% of silicon dioxide aerogel, 0.90% of defoaming agent and 62.90% of waterborne polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 36.40% of nano titanium dioxide and 63.60% of nano silica sol.
Example 3:
different from the examples 1-2, the material comprises the following components in percentage by weight: 12.10% of wood fiber, 8.60% of cotton fiber, 20.50% of polytetrafluoroethylene, 23.10% of epoxy resin, 5.40% of composite modified filler A, 14.80% of composite modified filler B and 15.50% of organic solvent; the composite modified filler A comprises the following components in percentage by weight: 35.80% of silicon dioxide aerogel, 0.85% of defoaming agent and 63.35% of aqueous polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 35.30 percent of nano titanium dioxide and 64.70 percent of nano silicon dioxide sol.
Respectively taking the highland barley paper for lithium battery packaging prepared in the above examples 1-3, the highland barley paper for lithium battery packaging of the first control group, the highland barley paper for lithium battery packaging of the second control group, the highland barley paper for lithium battery packaging of the third control group, the highland barley paper for lithium battery packaging of the fourth control group and the highland barley paper for lithium battery packaging of the fifth control group, wherein the highland barley paper for lithium battery packaging of the first control group has no silica aerogel compared with the examples, the highland barley paper for lithium battery packaging of the second control group has no aqueous polyurethane resin compared with the examples, the highland barley paper for lithium battery packaging of the third control group has no nano titanium dioxide compared with the examples, the highland barley paper for lithium battery packaging of the fourth control group has no nano silica sol compared with the examples, and the highland barley paper for lithium battery packaging of the three examples and the highland barley paper for lithium battery packaging of the four control groups are respectively tested in seven groups, testing every 30 samples in one group; the test results are shown in table one:
table one:
Figure BDA0003210290560000061
Figure BDA0003210290560000071
as can be seen from the table I, when the raw material ratio of the highland barley paper for lithium battery packaging is as follows: comprises the following components in percentage by weight: 12.10% of wood fiber, 8.60% of cotton fiber, 20.50% of polytetrafluoroethylene, 23.10% of epoxy resin, 5.40% of composite modified filler A, 14.80% of composite modified filler B and 15.50% of organic solvent; the composite modified filler A comprises the following components in percentage by weight: 35.80% of silicon dioxide aerogel, 0.85% of defoaming agent and 63.35% of aqueous polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 35.30 percent of nano titanium dioxide and 64.70 percent of nano silicon dioxide sol can effectively improve the high and low temperature resistance of the highland barley paper, and can ensure that the highland barley paper can be rapidly switched under high and low temperature environments and then ensure the waterproof performance of the highland barley paper; embodiment 3 is a preferred embodiment of the present invention, the wood fiber, the cotton fiber and the polytetrafluoroethylene in the formula are used as the main materials of the highland barley paper base material, and the composite fiber b and the composite fiber d are compounded into the highland barley paper base material, so that the temperature change resistance, the flame retardant property and the waterproof property of the highland barley paper base material can be effectively enhanced; the silica aerogel and the waterborne polyurethane resin in the composite modified filler A are blended and compounded, and then are blended with the organic solvent and then are subjected to electrostatic spinning to prepare silica aerogel and waterborne polyurethane resin composite fibers, so that the temperature change resistance, the waterproof performance and the flame retardant performance of the composite fibers b can be effectively ensured, the composite fibers b are mixed with the epoxy resin and the organic solvent to prepare an intermediate protective film, and the intermediate protective film is coated outside the highland barley paper; the nano titanium dioxide and the nano silica sol in the composite modified filler B are blended and compounded, the nano titanium dioxide can obviously inhibit the accumulation of surface charges of an aged insulating paperboard, and then the nano titanium dioxide and the nano silica sol composite fiber is prepared by blending with an organic solvent and then electrostatic spinning, so that the temperature change resistance, the waterproof performance and the flame retardant performance of the composite fiber d are effectively ensured.
Example 4:
the invention provides highland barley paper for lithium battery packaging, which comprises the following components in percentage by weight: 12.10% of wood fiber, 8.60% of cotton fiber, 20.50% of polytetrafluoroethylene, 23.10% of epoxy resin, 5.40% of composite modified filler A, 14.80% of composite modified filler B and 15.50% of organic solvent; the composite modified filler A comprises the following components in percentage by weight: 35.80% of silicon dioxide aerogel, 0.85% of defoaming agent and 63.35% of aqueous polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 35.30 percent of nano titanium dioxide and 64.70 percent of nano silicon dioxide sol;
the organic solvent is one or two of butyl acetate, isobutyl acetate, n-propanol and tert-butanol;
the invention also provides a preparation method of the highland barley paper for lithium battery packaging, which comprises the following specific preparation steps:
the method comprises the following steps: weighing the wood fiber, the cotton fiber, the polytetrafluoroethylene, the epoxy resin, the composite modified filler A, the composite modified filler B and the organic solvent in parts by weight;
step two: pulping the wood fibers and the cotton fibers in the step one to obtain pulp;
step three: stirring and mixing the composite modified filler A in the step one and one eighth of the organic solvent by weight, and carrying out ultrasonic treatment for 15 minutes to obtain a mixture a;
step four: carrying out electrostatic spinning treatment on the mixture a prepared in the third step to obtain composite fibers b;
step five: stirring and mixing the composite modified filler B in the step one and one fifth of the organic solvent by weight, and carrying out ultrasonic treatment for 20 minutes at the same time to obtain a mixture c;
step six: performing electrostatic spinning treatment on the mixture c prepared in the fifth step to obtain composite fibers d;
step seven: adding the polytetrafluoroethylene in the step one, one-half of the organic solvent in parts by weight, one-third of the composite fiber b prepared in the step four and one-third of the composite fiber d prepared in the step six into the slurry prepared in the step two together, and carrying out ultrasonic treatment for 25 minutes to obtain a mixture e;
step eight: mixing one third of the epoxy resin in the first step, one tenth of the organic solvent in the first step and the composite fiber b prepared in the fourth step, and performing ultrasonic treatment for 25 minutes to obtain a mixture f;
step nine: mixing two thirds of the epoxy resin, the rest of the organic solvent and the rest of the composite fiber d prepared in the sixth step in parts by weight in the first step, and performing ultrasonic treatment for 25 minutes to obtain a mixture g;
step ten: processing the mixture e prepared in the step seven by using a double-screw extruder to prepare a highland barley paper base material, and respectively processing the mixture f prepared in the step eight by using a film blowing machine to prepare an intermediate protective film; respectively processing the mixture g prepared in the ninth step by using a film blowing machine to prepare an outer protective film;
step eleven: performing film coating processing on the outside of the highland barley paper base material: and (3) coating the middle protective films on two sides of the outside of the highland barley paper base material, and coating the outer protective films on the outer sides of the middle protective films to prepare the highland barley paper for lithium battery packaging.
In the third step, the ultrasonic frequency is 1.4MHz, and the ultrasonic power is 300W; in the fourth step, 12KV high voltage is applied in the electrostatic spinning process, the distance between a capillary nozzle of the injector and a grounded receiving device is 8cm, and the flow rate of the spinning solution is 1.1 ml/h; in the fifth step, the ultrasonic frequency is 1.7MHz, and the ultrasonic power is 300W; in the sixth step, in the electrostatic spinning process, 12KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 10cm, and the flow rate of the spinning solution is 1.2 ml/h; in the seventh step, the eighth step and the ninth step, the ultrasonic frequency is 1.7MHz, and the ultrasonic power is 300W.
Example 5:
different from the embodiment 4, in the third step, the ultrasonic frequency is 1.8MHz, and the ultrasonic power is 500W; in the fourth step, 14KV high voltage is applied in the electrostatic spinning process, the distance between a capillary nozzle of the injector and a grounded receiving device is 10cm, and the flow rate of the spinning solution is 1.5 ml/h; in the fifth step, the ultrasonic frequency is 1.9MHz, and the ultrasonic power is 400W; in the sixth step, 14KV high voltage is applied in the electrostatic spinning process, the distance between a capillary nozzle of the injector and a grounded receiving device is 12cm, and the flow rate of the spinning solution is 1.8 ml/h; in the seventh step, the eighth step and the ninth step, the ultrasonic frequency is 1.9MHz, and the ultrasonic power is 400W.
Example 6:
different from the embodiments 4-5, in the third step, the ultrasonic frequency is 1.6MHz, and the ultrasonic power is 400W; in the fourth step, in the electrostatic spinning process, 13KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 9cm, and the flow rate of the spinning solution is 1.3 ml/h; in the fifth step, the ultrasonic frequency is 1.8MHz, and the ultrasonic power is 350W; in the sixth step, in the electrostatic spinning process, 13KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 11cm, and the flow rate of the spinning solution is 1.5 ml/h; in the seventh step, the eighth step and the ninth step, the ultrasonic frequency is 1.8MHz, and the ultrasonic power is 350W.
Taking the highland barley paper for lithium battery encapsulation prepared in the above examples 4-6, the highland barley paper for lithium battery encapsulation of the fifth control group, the highland barley paper for lithium battery encapsulation of the sixth control group, the highland barley paper for lithium battery encapsulation of the seventh control group, the highland barley paper for lithium battery encapsulation of the eighth control group, the highland barley paper for lithium battery encapsulation of the ninth control group and the highland barley paper for lithium battery encapsulation of the tenth control group, respectively, directly mixing all the raw materials compared with the examples, and then carrying out extrusion molding, wherein the highland barley paper for lithium battery encapsulation of the sixth control group has no operation in the third step compared with the examples, the highland barley paper for lithium battery encapsulation of the seventh control group has no operation in the fourth step compared with the examples, the highland barley paper for lithium battery encapsulation of the eighth control group has no operation in the fifth step compared with the examples, and the highland barley paper for lithium battery encapsulation of the ninth control group has no operation in the sixth step compared with the examples, compared with the embodiments, the highland barley paper for lithium battery encapsulation of the comparison group ten has no operation in the step seven, the highland barley paper for lithium battery encapsulation prepared in the three embodiments and the highland barley paper for lithium battery encapsulation of the six comparison groups are respectively tested in nine groups, each 30 samples are taken as one group for testing, and the test results are shown in the table two:
table two:
Figure BDA0003210290560000101
Figure BDA0003210290560000111
as can be seen from table two, example 6 is a preferred embodiment of the present invention; in the second step, wood fibers and cotton fibers are subjected to pulping processing treatment to obtain pulp; in the third step, the composite modified filler A and the organic solvent are mixed for 1.6MHz ultrasonic treatment, so that the silicon dioxide aerogel, the defoaming agent and the waterborne polyurethane resin are mixed more uniformly, the subsequent electrostatic spinning processing is ensured, and the stability and the structural uniformity of the composite fiber b are ensured; in the fourth step, the mixture a is subjected to electrostatic spinning treatment, so that the rapid compounding of the silicon dioxide aerogel and the waterborne polyurethane resin is ensured, and the temperature change resistance, the waterproof performance and the flame retardant performance of the composite fiber b are ensured; in the fifth step, the composite modified filler B and the organic solvent are mixed for 1.8MHz ultrasonic treatment, so that the nano titanium dioxide and the nano silicon dioxide sol are mixed more uniformly, the subsequent electrostatic spinning processing is facilitated, and the stability and the structural uniformity of the composite fiber d are ensured; in the sixth step, the mixture c is subjected to electrostatic spinning treatment, so that the rapid compounding of the nano titanium dioxide and the nano silicon dioxide sol is ensured, and the temperature change resistance, the waterproof performance and the flame retardant performance of the composite fiber d are ensured; in the seventh step, the sizing agent, the polytetrafluoroethylene, the organic solvent, the composite fiber b and the composite fiber d are blended, and the composite fiber b and the composite fiber d are added into the highland barley paper base material, so that the temperature change resistance, the waterproof performance and the flame retardant performance of the highland barley paper base material can be effectively enhanced; in the tenth step, the composite fiber b is used as a main raw material to prepare an intermediate protective film, and the composite fiber d is used as a main raw material to prepare an outer protective film; in the eleventh step, the highland barley paper with a five-layer structure is prepared, and the temperature change resistance, the waterproof performance and the flame retardant performance of the highland barley paper can be further enhanced.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The highland barley paper for lithium battery packaging is characterized in that: comprises the following components in percentage by weight: 11.40-12.80% of wood fiber, 8.30-8.90% of cotton fiber, 20.30-20.70% of polytetrafluoroethylene, 22.40-23.80% of epoxy resin, 5.20-5.60% of composite modified filler A, 14.40-15.20% of composite modified filler B and the balance of organic solvent.
2. The highland barley paper for lithium battery packaging as claimed in claim 1, wherein: the composite modified filler A comprises the following components in percentage by weight: 35.40-36.20% of silicon dioxide aerogel, 0.80-0.90% of defoaming agent and the balance of waterborne polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 34.20-36.40% of nano titanium dioxide, and the balance of nano silicon dioxide sol.
3. The highland barley paper for lithium battery packaging as claimed in claim 2, wherein: comprises the following components in percentage by weight: 11.40% of wood fiber, 8.30% of cotton fiber, 20.30% of polytetrafluoroethylene, 22.40% of epoxy resin, 5.20% of composite modified filler A, 14.40% of composite modified filler B and 18.00% of organic solvent; the composite modified filler A comprises the following components in percentage by weight: 35.40% of silicon dioxide aerogel, 0.80% of defoaming agent and 63.80% of waterborne polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 34.20 percent of nano titanium dioxide and 65.80 percent of nano silicon dioxide sol.
4. The highland barley paper for lithium battery packaging as claimed in claim 2, wherein: comprises the following components in percentage by weight: 12.80% of wood fiber, 8.90% of cotton fiber, 20.70% of polytetrafluoroethylene, 23.80% of epoxy resin, 5.60% of composite modified filler A, 15.20% of composite modified filler B and 13.00% of organic solvent; the composite modified filler A comprises the following components in percentage by weight: 36.20% of silicon dioxide aerogel, 0.90% of defoaming agent and 62.90% of waterborne polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 36.40% of nano titanium dioxide and 63.60% of nano silica sol.
5. The highland barley paper for lithium battery packaging as claimed in claim 2, wherein: comprises the following components in percentage by weight: 12.10% of wood fiber, 8.60% of cotton fiber, 20.50% of polytetrafluoroethylene, 23.10% of epoxy resin, 5.40% of composite modified filler A, 14.80% of composite modified filler B and 15.50% of organic solvent; the composite modified filler A comprises the following components in percentage by weight: 35.80% of silicon dioxide aerogel, 0.85% of defoaming agent and 63.35% of aqueous polyurethane resin; the composite modified filler B comprises the following components in percentage by weight: 35.30 percent of nano titanium dioxide and 64.70 percent of nano silicon dioxide sol.
6. The highland barley paper for lithium battery packaging as claimed in claim 1, wherein: the organic solvent is one or two of butyl acetate, isobutyl acetate, n-propanol and tert-butanol.
7. The preparation method of the highland barley paper for lithium battery packaging as claimed in any one of claims 1 to 6, wherein the highland barley paper comprises the following steps: the preparation method comprises the following specific steps:
the method comprises the following steps: weighing the wood fiber, the cotton fiber, the polytetrafluoroethylene, the epoxy resin, the composite modified filler A, the composite modified filler B and the organic solvent in parts by weight;
step two: pulping the wood fibers and the cotton fibers in the step one to obtain pulp;
step three: stirring and mixing the composite modified filler A in the step one and one eighth of the organic solvent by weight, and carrying out ultrasonic treatment for 10-20 minutes to obtain a mixture a;
step four: carrying out electrostatic spinning treatment on the mixture a prepared in the third step to obtain composite fibers b;
step five: stirring and mixing the composite modified filler B in the step one and one fifth of the organic solvent by weight, and carrying out ultrasonic treatment for 15-25 minutes to obtain a mixture c;
step six: performing electrostatic spinning treatment on the mixture c prepared in the fifth step to obtain composite fibers d;
step seven: adding the polytetrafluoroethylene in the step one, a half of the organic solvent in parts by weight, a third of the composite fiber b prepared in the step four and a third of the composite fiber d prepared in the step six into the slurry prepared in the step two together, and carrying out ultrasonic treatment for 20-30 minutes to obtain a mixture e;
step eight: mixing one third of the epoxy resin, one tenth of the organic solvent and the composite fiber b prepared in the fourth step in the first step, and performing ultrasonic treatment for 20-30 minutes to obtain a mixture f;
step nine: mixing two thirds of the epoxy resin, the rest of the organic solvent and the rest of the composite fiber d prepared in the sixth step in parts by weight in the first step, and performing ultrasonic treatment for 20-30 minutes to obtain a mixture g;
step ten: processing the mixture e prepared in the step seven by using a double-screw extruder to prepare a highland barley paper base material, and respectively processing the mixture f prepared in the step eight by using a film blowing machine to prepare an intermediate protective film; respectively processing the mixture g prepared in the ninth step by using a film blowing machine to prepare an outer protective film;
step eleven: performing film coating processing on the outside of the highland barley paper base material: and (3) coating the middle protective films on two sides of the outside of the highland barley paper base material, and coating the outer protective films on the outer sides of the middle protective films to prepare the highland barley paper for lithium battery packaging.
8. The preparation method of the highland barley paper for lithium battery packaging as claimed in claim 7, which is characterized in that: in the third step, the ultrasonic frequency is 1.4-1.8 MHz, and the ultrasonic power is 300-500W; in the fourth step, in the electrostatic spinning process, 12-14 KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 8-10 cm, and the flow speed of the spinning solution is 1.1-1.5 ml/h; in the fifth step, the ultrasonic frequency is 1.7-1.9 MHz, and the ultrasonic power is 300-400W; in the sixth step, in the electrostatic spinning process, 12-14 KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 10-12 cm, and the flow rate of the spinning solution is 1.2-1.8 ml/h; in the seventh step, the eighth step and the ninth step, the ultrasonic frequency is 1.7-1.9 MHz, and the ultrasonic power is 300-400W.
9. The preparation method of the highland barley paper for lithium battery packaging as claimed in claim 8, which is characterized in that: in the third step, the ultrasonic frequency is 1.4MHz, and the ultrasonic power is 300W; in the fourth step, 12KV high voltage is applied in the electrostatic spinning process, the distance between a capillary nozzle of the injector and a grounded receiving device is 8cm, and the flow rate of the spinning solution is 1.1 ml/h; in the fifth step, the ultrasonic frequency is 1.7MHz, and the ultrasonic power is 300W; in the sixth step, in the electrostatic spinning process, 12KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 10cm, and the flow rate of the spinning solution is 1.2 ml/h; in the seventh step, the eighth step and the ninth step, the ultrasonic frequency is 1.7MHz, and the ultrasonic power is 300W.
10. The preparation method of the highland barley paper for lithium battery packaging as claimed in claim 8, which is characterized in that: in the third step, the ultrasonic frequency is 1.6MHz, and the ultrasonic power is 400W; in the fourth step, in the electrostatic spinning process, 13KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 9cm, and the flow rate of the spinning solution is 1.3 ml/h; in the fifth step, the ultrasonic frequency is 1.8MHz, and the ultrasonic power is 350W; in the sixth step, in the electrostatic spinning process, 13KV high voltage is applied, the distance between a capillary nozzle of the injector and a grounded receiving device is 11cm, and the flow rate of the spinning solution is 1.5 ml/h; in the seventh step, the eighth step and the ninth step, the ultrasonic frequency is 1.8MHz, and the ultrasonic power is 350W.
CN202110930169.7A 2021-08-13 2021-08-13 Highland barley paper for lithium battery packaging and preparation method thereof Pending CN113832776A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102585360A (en) * 2011-12-31 2012-07-18 李松 Composite plastic, manufacturing method and encapsulation shell, lithium battery and battery pack manufactured by using composite plastic
CN108035074A (en) * 2017-12-29 2018-05-15 厦门大学 A kind of preparation method of aerosil nano-fiber composite film
CN108565383A (en) * 2018-05-03 2018-09-21 东莞理工学院 A kind of high tenacity lithium battery diaphragm and preparation method thereof
CN111040547A (en) * 2019-12-27 2020-04-21 苏州晟德亿节能环保科技有限公司 Thermal insulation aerogel coating and preparation method thereof
CN112787041A (en) * 2020-04-24 2021-05-11 深圳市劢全新材料科技有限责任公司 Composite diaphragm for lithium battery and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102585360A (en) * 2011-12-31 2012-07-18 李松 Composite plastic, manufacturing method and encapsulation shell, lithium battery and battery pack manufactured by using composite plastic
CN108035074A (en) * 2017-12-29 2018-05-15 厦门大学 A kind of preparation method of aerosil nano-fiber composite film
CN108565383A (en) * 2018-05-03 2018-09-21 东莞理工学院 A kind of high tenacity lithium battery diaphragm and preparation method thereof
CN111040547A (en) * 2019-12-27 2020-04-21 苏州晟德亿节能环保科技有限公司 Thermal insulation aerogel coating and preparation method thereof
CN112787041A (en) * 2020-04-24 2021-05-11 深圳市劢全新材料科技有限责任公司 Composite diaphragm for lithium battery and preparation method thereof

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