CN110592802B - Method for manufacturing zinc-manganese battery diaphragm regenerated cellulose membrane - Google Patents
Method for manufacturing zinc-manganese battery diaphragm regenerated cellulose membrane Download PDFInfo
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- CN110592802B CN110592802B CN201910726509.7A CN201910726509A CN110592802B CN 110592802 B CN110592802 B CN 110592802B CN 201910726509 A CN201910726509 A CN 201910726509A CN 110592802 B CN110592802 B CN 110592802B
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- regenerated cellulose
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- cellulose membrane
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/425—Cellulose series
- D04H1/4258—Regenerated cellulose series
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a method for manufacturing a zinc-manganese battery diaphragm regenerated cellulose membrane, wherein anti-sticking particles which are spherical bulges are attached to the surface of a regenerated cellulose-based membrane, the mass percent of the anti-sticking particles in the regenerated cellulose-based membrane is 0.01-0.05%, and the mass percent of the moisture in the regenerated cellulose-based membrane is 4-7%, so that the battery diaphragm paper is biodegradable, light, moderate in hardness, high-temperature resistant, good in air permeability, lyophilic and dimensional stability. The invention is composed of regenerated cellulose component and moisture and antisticking component for keeping flexibility of film, light in weight, natural degradable, possessing ideal transparency and glossiness, high temperature resistance, high lyophilic property and good dimensional stability, it can reduce attenuation of initial voltage, prolong service life of alkaline battery.
Description
Technical Field
The invention belongs to the fields of regenerated cellulose membranes, preparation technologies thereof and battery technologies, and particularly relates to a method for manufacturing regenerated cellulose membrane battery diaphragm paper.
Background
In recent years, significant advances have been made in battery technology through the continuing development of electrochemistry and emerging battery chemistries. However, to date there has not been an "ideal" battery that performs well under a variety of operating conditions. This situation also occurs with separators, and to date, there has not been an "ideal" separator that fully meets the chemical and geometric requirements of the battery. The separator of the battery is a major constituent of the battery. The separator has only an initial function of separating the positive electrode and the negative electrode without causing a short circuit. With the advent of various battery systems and the demand for battery use, the role of battery separators has continued to expand, and the demand for battery separators has continued to increase. The quality of the battery diaphragm directly influences the internal resistance, discharge capacity and safety performance of the battery, and the service life of the battery is often determined by the battery diaphragm.
At present, the mainstream product of the battery separator material is a polyolefin separator, which has high strength and good chemical stability, and as a thermoplastic material, porous polyolefin has a self-closing function of shrinkage porosity at a temperature higher than the glass transition temperature, so that the impedance is significantly increased, the current passing through the battery is limited, and the phenomena such as explosion caused by overheating can be prevented, so that the battery separator is a relatively reliable separator material. Another more important problem of the polyolefin material separator is the safety of high-power discharge, the size deformation of the material is obvious at high temperature, the melting point is generally lower than 170 ℃, and when the local heat of the battery reaches the temperature, the separator can be rapidly melted, so that the anode and the cathode are rapidly contacted, and thermal runaway behavior occurs. Research shows that the high-melting-point fiber reinforced diaphragm or the diaphragm prepared by the material with higher melting point can well improve the thermal melting temperature of the diaphragm, thereby effectively ensuring the safety of the battery.
Disclosure of Invention
The purpose of the invention is as follows: in view of the above technical requirements, the present invention aims to provide a biodegradable battery separator paper with light weight, moderate hardness, high temperature resistance, good air permeability, good hydrophilicity and good dimensional stability for a regenerated cellulose membrane.
The regenerated cellulose membrane is made of natural cellulose as a raw material into viscose; then, the original film is prepared by film forming, solidification and regeneration through a special process; the raw membrane is subjected to alkalization, bleaching and water washing, but before plasticizing bath treatment and drying, the raw membrane is dipped and coated in anti-adhesion particle latex, so that the adhesion resistance particles are adhered to the two sides of the regenerated cellulose membrane, the anti-adhesion purpose is achieved, and the battery diaphragm paper is finally prepared.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the technical scheme that:
a manufacturing method of a zinc-manganese battery diaphragm regenerated cellulose membrane comprises the following steps:
step one, manufacturing viscose fibers by dissolving pulp and required chemical reagents. The viscose fiber reaches the molding requirement through ripening, filtering, defoaming and spinning;
injecting the prepared polyalcohol solution into a pipeline in front of a viscose filter according to the flow calculated by the vehicle speed, wherein the flow is 100-200mL/min, then carrying out coagulation reaction on the viscose in a No. 1 tank acid bath, carrying out a series of chemical and water washing treatments, and carrying out anti-sticking bath treatment before entering a drying section to meet the anti-sticking requirement;
step three, controlling the curling speed of the molding dry part to be 35-50m/min, and carefully controlling the temperature, the speed and the moisture of a finished product in the drying process;
and step four, after the drying temperature of the dry part is molded and dried, and the physical indexes are detected to be qualified, the regenerated cellulose membrane battery diaphragm paper is obtained.
As an optimization: in the first step, the dissolving pulp comprises wood pulp, straw pulp, cotton pulp, hemp pulp, bamboo pulp and bagasse pulp; wherein the alpha-cellulose content of the pulp is more than or equal to 90 percent, and the polymerization degree is more than or equal to 600.
As an optimization: in the second step, in the anti-sticking bath treatment, the anti-sticking agent comprises gas-phase silica sol and liquid-phase silica sol.
As an optimization: in the second step, in the anti-sticking process, the conventional plasticizer treatment is not carried out according to the requirement of the battery diaphragm.
As an optimization: in the third step, the drying temperature of the dry part is between 75 and 140 ℃.
The regenerated cellulose-based membrane manufactured according to the manufacturing method of the zinc-manganese battery diaphragm regenerated cellulose membrane is characterized in that anti-adhesion particles protruding in a spherical shape are attached to the surface of the regenerated cellulose-based membrane, the anti-adhesion particles account for 0.01-0.05% of the regenerated cellulose-based membrane by mass, and the moisture contained in the regenerated cellulose-based membrane accounts for 4-7% of the regenerated cellulose-based membrane by mass.
As an optimization: the anti-sticking particles are modified cationic silica, and the particle size of the anti-sticking agent particles is 300-600nm
As an optimization: the thickness of the regenerated cellulose-based membrane is 30-40um.
As an optimization: the regenerated cellulose-based membrane resists high temperature up to 200 ℃.
As an optimization: the quantitative amount of the regenerated cellulose membrane battery diaphragm paper is 46-50g/m 2 The tensile strength is more than or equal to 60N/15mm, and the elongation is more than or equal to 8 percent.
Has the advantages that: compared with the prior common battery diaphragm paper, the invention has the following advantages:
the invention is composed of regenerated cellulose component and moisture and antisticking component for keeping flexibility of membrane, it is light, degradable, has ideal transparency and glossiness, high temperature resistance, high lyophilic and good dimensional stability, it can reduce attenuation of initial voltage, prolong service life of alkaline battery.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, so that those skilled in the art can better understand the advantages and features of the present invention, and thus the protection scope of the present invention is more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Examples
The present invention is further illustrated by the following specific examples, but the embodiments of the present invention are not limited thereto, and the process parameters not specifically indicated may be performed by referring to the conventional techniques.
A method for manufacturing a zinc-manganese battery diaphragm regenerated cellulose membrane comprises the following steps:
step one, manufacturing viscose fibers by dissolving pulp and required chemical reagents. The viscose fiber reaches the molding requirement through ripening, filtering, defoaming and spinning; the dissolving pulp comprises wood pulp, straw pulp, cotton pulp, hemp pulp, bamboo pulp and bagasse pulp; wherein the content of alpha-cellulose in the pulp is more than or equal to 90 percent, and the polymerization degree is more than or equal to 600.
Injecting the prepared polyalcohol solution into a pipeline in front of a viscose filter according to the flow calculated by the vehicle speed, wherein the flow is 100-200mL/min, then carrying out coagulation reaction on the viscose in a No. 1 tank acid bath, carrying out a series of chemical and water washing treatments, and carrying out anti-sticking bath treatment to meet the anti-sticking requirement before entering a drying section, and not carrying out conventional plasticizer treatment according to the requirement of a battery diaphragm; in the anti-sticking bath treatment, the anti-sticking agent comprises gas-phase silica sol and liquid-phase silica sol.
Thirdly, controlling the curling speed of the molding dry part to be 35-50m/min, and carefully controlling the temperature, the speed and the moisture of the finished product in the drying process, wherein the drying temperature of the dry part is 75-140 ℃;
and step four, after the drying temperature of the dry part is molded and dried, and the physical indexes are detected to be qualified, so that the regenerated cellulose membrane battery diaphragm paper is obtained.
In this embodiment, the anti-sticking particles protruding in a spherical shape are attached to the surface of the regenerated cellulose-based membrane, the anti-sticking particles account for 0.01 to 0.05% by mass of the regenerated cellulose-based membrane, and the moisture contained in the regenerated cellulose-based membrane accounts for 4 to 7% by mass of the regenerated cellulose-based membrane.
The anti-sticking particles are modified cationic silica, the particle size of the anti-sticking agent particles is 300-600nm, and the thickness of the regenerated cellulose-based membrane is 30-40um. The regenerated cellulose base membrane resists high temperature up to 200 ℃. The quantitative amount of the regenerated cellulose membrane battery diaphragm paper is 46-50g/m 2 The tensile strength is more than or equal to 60N/15mm, and the elongation is more than or equal to 8 percent.
The specific embodiment is as follows:
(1) Putting a batch of pulp into alkalization at 50 deg.C for 30min. After pressing, the mixture was aged for 6 hours in an aging drum at a total aging temperature of 230 ℃. Then yellowing is carried out for 1h at the temperature of 30 ℃. Then ripening at 20 ℃, and preparing viscose fiber for standby after spinning.
(2) The injection flow rate of the polyalcohol solution is 150ml/min. The viscose fiber is regenerated into a film in a forming No. 1 tank, and the water bath temperature of a No. 2-8 tank is controlled to be 90 ℃. The water flow of the washing water is 2m 3 H is used as the reference value. The 18# tank is subjected to anti-sticking treatment by an anti-sticking agent, and the concentration of the anti-sticking agent is 1g/L.
(3) The forming speed is controlled at 45m/min, the drying initial temperature is 130 ℃, then the drying temperature of each zone is decreased progressively, and the drying finishing temperature is 80 ℃.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the present invention as defined in the accompanying claims.
Claims (1)
1. A manufacturing method of a zinc-manganese battery diaphragm regenerated cellulose membrane is characterized by comprising the following steps: the method comprises the following steps:
step one, manufacturing viscose fibers by dissolving pulp and required chemical reagents; alkalizing a batch of pulp at 50 ℃ for 30min, squeezing, aging in an aging drum for 6h at a total aging temperature of 230 ℃, and yellowing at 30 ℃ for 1h; then ripening at 20 ℃, and preparing viscose fiber for later use after spinning; the dissolving pulp comprises wood pulp, straw pulp, cotton pulp, hemp pulp, bamboo pulp and bagasse pulp; wherein the content of alpha-cellulose in the pulp is more than or equal to 90 percent, and the polymerization degree is more than or equal to 600;
step two, injecting the prepared polyalcohol solution into a pipeline in front of a viscose filter according to the flow calculated by the vehicle speed, wherein the injection flow of the polyalcohol solution is 150ml/min, the viscose fiber regenerates a film in a forming No. 1 tank, the water bath temperature of a No. 2-8 tank is controlled to be 90 ℃, and the water flow of washing water is 2m 2 The 18# groove is subjected to anti-sticking treatment by an anti-sticking agent, the concentration of the anti-sticking agent is 1g/L, anti-sticking bath treatment is carried out by adopting gas-phase silica sol, and conventional plasticizer treatment is not carried out according to the requirement of a battery diaphragm, so that the anti-sticking requirement is met;
step three, controlling the curling speed of the forming dry part at 45m/min, wherein the drying initial temperature is 130 ℃, then the drying temperature of each area is decreased progressively, and the drying finishing temperature is 80 ℃;
step four, after the drying temperature of the dry part is molded and dried, and the physical index is detected to be qualified, the regenerated cellulose membrane battery diaphragm paper is obtained; the anti-sticking particles which are spherical bulges are attached to the surface of the regenerated cellulose membrane, the mass percent of the anti-sticking particles in the regenerated cellulose membrane is 0.01-0.05%, and the mass percent of the water contained in the regenerated cellulose membrane is 4-7%; the anti-sticking particles are modified cationic silicon dioxide, and the particle size of the anti-sticking particles is 300-600nm; the thickness of the regenerated cellulose membrane is 30-40 μm; the regenerated cellulose membrane resists high temperature up to 200 ℃; the quantitative amount of the regenerated cellulose membrane battery diaphragm paper is 46-50g/m 2 The tensile strength is more than or equal to 60N/15mm, and the elongation is more than or equal to 8 percent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910726509.7A CN110592802B (en) | 2019-08-07 | 2019-08-07 | Method for manufacturing zinc-manganese battery diaphragm regenerated cellulose membrane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910726509.7A CN110592802B (en) | 2019-08-07 | 2019-08-07 | Method for manufacturing zinc-manganese battery diaphragm regenerated cellulose membrane |
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| CN110592802A CN110592802A (en) | 2019-12-20 |
| CN110592802B true CN110592802B (en) | 2022-01-04 |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504316B (en) * | 2011-11-07 | 2013-04-03 | 潍坊恒联玻璃纸有限公司 | Method for preparing regenerated cellulose membrane |
| CN102504313B (en) * | 2011-11-07 | 2013-07-17 | 潍坊恒联玻璃纸有限公司 | Method for semi-permeable heat-sealed regenerated cellulose membrane |
| US20190044129A1 (en) * | 2016-02-02 | 2019-02-07 | Research Foundation Of The City University Of New York | Rechargeable Alkaline Manganese Dioxide-Zinc Bipolar Batteries |
| CN106207053B (en) * | 2016-09-29 | 2018-07-24 | 河南科高辐射化工科技有限公司 | Preparation method of alkaline zinc-manganese battery diaphragm based on nanocellulose |
| CN206516691U (en) * | 2016-11-30 | 2017-09-22 | 山东恒联新材料股份有限公司 | A kind of battery separator paper |
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