阅读说明：本技术 改性水化纤维素—维尼纶复合隔膜纸制备方法及电池中应用 (It is applied in modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper and battery ) 是由 *** 张宁 关海波 景义军 于 2018-05-25 设计创作，主要内容包括：本发明涉及改性水化纤维素—维尼纶复合隔膜纸制备方法及电池中应用。本发明属于电化学技术领域。改性水化纤维素—维尼纶复合隔膜纸制备方法,其制备过程：(1)用重量份数为4-6:1:9-11的乙醇、氢氧化钾和纯水配制成皂化液,加热到45～50℃,三醋酸纤维素皂化,用纯水洗至中性；(2)取重量份数为55-75份改性水化纤维素放入打浆机,经疏解、打浆,得到改性水化纤维素浆料；(3)取重量份数为25-45的维尼纶纤维,加水、搅拌、疏解至纤维完全分散；(4)改性水化纤维素浆料和维尼纶纤维浆料全部配浆,加水、分散剂,搅拌；混合浆料脱水成型、压榨、施胶、干燥、热压成型,再经卷纸、切割。本发明可得到激活时间1.5s、最长工作寿命大于3h的锌银贮备电池隔膜。(The present invention relates to apply in modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper and battery.The invention belongs to electrochemical technology fields.Modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper, its preparation process: (1) ethyl alcohol, potassium hydroxide and the pure water that are 4-6:1:9-11 with parts by weight are configured to saponification liquor, 45~50 DEG C are heated to, Triafol T saponification is washed till neutrality with pure water；(2) taking parts by weight is that 55-75 parts of modified cellulose hydrates are put into beater, is discongested, is beaten, and modified cellulose hydrate slurry is obtained；(3) taking parts by weight is the vinylon fiber of 25-45, adds water, stirs, discongests to fiber and be completely dispersed；(4) modified cellulose hydrate slurry and vinylon fiber slurry are all with slurry, add water, dispersing agent, stir；It is mixed slurry dehydration forming, squeezing, sizing, drying, hot-forming, then through roll paper, cutting.Activationary time 1.5s can be obtained in the present invention, maximum service life is greater than the zinc-silver reserve battery diaphragm of 3h.)

1. a kind of modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper, it is characterized in that: modified cellulose hydrate- Vinylon composite diaphragm paper preparation process:

(1) ethyl alcohol, potassium hydroxide and the pure water that are 4-6:1:9-11 with parts by weight are configured to saponification liquor, and saponification liquor is heated to 45~50 DEG C, Triafol T is put into saponification liquor and is saponified, saponification time is 20~30min, the aquation after saponification Cellulose is washed till neutrality with pure water, obtains modified cellulose hydrate；

(2) taking parts by weight is that 55-75 part modified cellulose hydrates are put into beater, fiber concentration 1-3% in water, through thin Solution, mashing obtain modified cellulose hydrate slurry；

(3) taking parts by weight is the vinylon fiber of 25-45, adds water, stirs, discongests to fiber and be completely dispersed, fiber is in water Concentration be 0.8-1.2%；

(4) modified cellulose hydrate slurry and vinylon fiber slurry are all with slurry, and adding water to mass percent concentration is 0.5%-0.7% is added the dispersing agent that mass concentration is 0.1%-1%, stirs evenly up to mixed slurry；Mixed slurry is in net It is portion's dehydration forming, squeezing, sizing, drying, hot-forming, then through roll paper, cutting to obtain modified cellulose hydrate-vinylon multiple Condensating fiber micro-pore septum paper.

2. modified cellulose hydrate according to claim 1-vinylon composite diaphragm Preparation Method made of paper, it is characterized in that: changing Property cellulose hydrate be put into beater after, first discongest 25~30min, be beaten 60-100min afterwards, stop when fiber dispersion is without slurry point Only mashing obtains modified cellulose hydrate slurry.

3. modified cellulose hydrate according to claim 1-vinylon composite diaphragm Preparation Method made of paper, it is characterized in that: dimension The fibre length of nylon fiber is 2mm-6mm, fiber number 0.4-0.6detx；The Triafol T degree of polymerization is 400~500.

4. modified cellulose hydrate according to claim 1-vinylon composite diaphragm Preparation Method made of paper, it is characterized in that: point Powder is carboxymethyl cellulose or polyacrylamide.

5. modified cellulose hydrate according to claim 1,2,3 or 4-vinylon composite diaphragm Preparation Method made of paper, special Sign is: the sizing agent of sizing by mass concentration be 2.0%~3.0% polyvinyl alcohol and concentration be 1.0%~2.0% starch by Etc. weight ratios be formulated；Hot-forming temperature is 170-200 DEG C, time 10-15min.

6. modified cellulose hydrate according to claim 5-vinylon composite diaphragm Preparation Method made of paper, it is characterized in that: changing The quantification of 55-65g/m of property cellulose hydrate-vinylon composite fibre micro-pore septum paper²。

7. modified cellulose hydrate according to claim 1-vinylon composite diaphragm paper is applied in the battery, feature Be: main diaphragm of the modified cellulose hydrate-vinylon composite diaphragm paper as zinc-silver reserve battery is tieed up with modified water chemical fibre Element-vinylon composite diaphragm paper bag covers zinc load, coats oxidation silver positive electrode with nylon yarn.

Technical field

The invention belongs to electrochemical technology fields, more particularly to a kind of modified cellulose hydrate-vinylon composite diaphragm It is applied in Preparation Method and battery made of paper.

Background technique

Currently, specific power is big since zinc-silver reserve battery has specific energy high, can be large current discharge, stable operating voltage, Voltage accuracy is high, and safety waits well unique feature.Zinc-silver oxide cell is widely used as the power supply in higher power device by countries in the world DC power supply.Long-life quickly activate zinc-silver reserve battery by gas generator, liquid reservoir, composite polar plate group, chemical heater, The components such as self-heating device, activation and heat-preservation control circuit, bonding wire socket, battery-pack exterior casing composition.It is connected when use by socket External activation power supply point fires gas generator, so that it is generated enough pressure, before the deadline by the electrolysis of separated storage Liquid injects in composite polar plate group, so that its activation is established electromotive force, and pass through the outside output voltage of bonding wire socket.

Long-life quickly activates zinc-silver reserve battery group to belong to chemical heat type zinc-silver reserve battery group, is generally used for primary In the quick response equipment of property, therefore working life is the key characteristic of battery pack after the activationary time of battery pack and activation, directly Connect the use demand for being related to that can battery pack meet electrical equipment.

The effect of diaphragm in the battery be isolated positive and negative electrode, adsorb after activation electrolyte, for participate in electrode reaction from Son provides migrating channels.Rapid infiltration of the electrolyte in diaphragm is one of the necessary condition that battery quickly activates, therefore diaphragm Rate of liquid aspiration speed directly affect the activationary time of battery；The electrolyte of zinc-silver reserve battery is the aqueous solution of potassium hydroxide, Belong to highly basic, has corrosiveness to diaphragm, the corrosion degradation speed of different diaphragms in the electrolytic solution is different, and diaphragm is by electrolyte The consequence of corrosion is strength reduction, and then battery short circuit is caused to fail；Meanwhile silver oxide has one in the aqueous solution of potassium hydroxide Fixed solubility, the silver oxide being dissolved in potassium hydroxide solution can be migrated through the micropore of diaphragm to cathode direction, work as migration When reaching a certain amount of, positive and negative anodes short circuit, battery failure will cause.Therefore the alkali corrosion resistance ability of diaphragm and the silver-colored transfer ability of resistance are Influence the principal element of battery service life.The main diaphragm that alkaline battery uses at present is divided into two classes, and one kind is alkali corrosion resistance energy Power and the stronger cellulose hydrate diaphragm of the silver-colored transfer ability of resistance, this kind of diaphragm is semi-permeable membrane, and aperture is small (nanoscale), electrolyte leaching It is slow to moisten speed；Another kind of is alkali corrosion resistance ability and the poor stationery diaphragm of the silver-colored transfer ability of resistance, the big (micron of this kind of membrane pore size Grade), electrolyte wetting velocity is fast.

And the available diaphragm of zinc-silver oxide cell cannot all be provided simultaneously with quick imbibition ability and strong alkali corrosion resistance energy at present Power and the silver-colored transfer ability of resistance, the activation performance of battery is associated, the working life of fast activated batteries with working life performance It is shorter, conversely, the activationary time of long-life batteries is relatively long.Currently known zinc-silver reserve battery diaphragm can only meet activation Time is the battery design of 1.5s, longest working time (wet service life) 3200s.

With the development of application market, which is no longer satisfied the demand of electrical equipment pair, exist need into One step improves the technical problems such as the working life of fast activation zinc-silver reserve battery group.

Summary of the invention

The present invention is to solve technical problem present in well-known technique and provide a kind of modified cellulose hydrate-vinylon It is applied in composite diaphragm Preparation Method made of paper and battery.

Zinc-silver reserve battery diaphragm of the present invention, will modified cellulose hydrate-vinylon composite fibre micro-pore septum paper as The main diaphragm of zinc-silver reserve battery.Zinc load is covered with modified cellulose hydrate-vinylon composite fibre micro-pore septum paper bag, is used Nylon yarn cladding oxidation silver positive electrode.The bulk composition of composite fibre micro-pore septum paper is that modified cellulose hydrate and vinylon are fine Dimension.

An object of the present invention is to provide a kind of with the object of the present invention is to provide one kind to have simple process, operation Conveniently, the modification aquation for the features such as zinc-silver reserve battery diaphragm of activationary time 1.5s, maximum service life greater than 3h can be obtained Cellulose-vinylon composite diaphragm Preparation Method made of paper.

There is the present invention modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper to be adopted the technical scheme that:

A kind of modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper, its main feature is that: modified water chemical fibre dimension Element-vinylon composite diaphragm paper preparation process:

(1) ethyl alcohol, potassium hydroxide and the pure water that are 4-6:1:9-11 with parts by weight are configured to saponification liquor, by saponification liquor plus Triafol T is put into saponification liquor and is saponified to 45~50 DEG C by heat, and saponification time is 20~30min, after saponification Cellulose hydrate is washed till neutrality with pure water, obtains modified cellulose hydrate；

(2) taking parts by weight is that 55-75 parts of modified cellulose hydrates are put into beater, fiber concentration 1-3% in water, It discongested, be beaten, obtain modified cellulose hydrate slurry；

(3) taking parts by weight is the vinylon fiber of 25-45, adds water, stirs, discongests to fiber and be completely dispersed, fiber exists Concentration in water is 0.8-1.2%；

(4) modified cellulose hydrate slurry and vinylon fiber slurry are all with slurry, and adding water to mass percent concentration is 0.5%-0.7% is added the dispersing agent that mass concentration is 0.1%-1%, stirs evenly up to mixed slurry；Mixed slurry is in net It is portion's dehydration forming, squeezing, sizing, drying, hot-forming, then through roll paper, cutting to obtain modified cellulose hydrate-vinylon multiple Condensating fiber micro-pore septum paper.

There is the present invention modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper can also use following technology Scheme:

Described has slow modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper, its main feature is that: modified water After cellulose is put into beater, 25~30min is first discongested, 60-100min is beaten afterwards, stops beating when fiber dispersion is without slurry point Slurry obtains modified cellulose hydrate slurry.

Described has slow modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper, its main feature is that: vinylon The fibre length of fiber is 2mm-6mm, fiber number 0.4-0.6detx；The Triafol T degree of polymerization is 400~500.

Described has slow modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper, its main feature is that: dispersing agent For carboxymethyl cellulose or polyacrylamide.

Described has slow modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper, its main feature is that: sizing is used Sizing agent by mass concentration be 2.0%~3.0% polyvinyl alcohol and concentration be 1.0%~2.0% starch by etc. weight ratios match It makes；Hot-forming temperature is 170-200 DEG C, time 10-15min.

Described has slow modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper, its main feature is that: modified water The quantification of 55-65g/m of cellulose-vinylon composite fibre micro-pore septum paper²。

The second object of the present invention is to provide a kind of modified cellulose hydrate-vinylon composite diaphragm paper to answer in the battery With slow modified cellulose hydrate-vinylon composite diaphragm paper is greater than the zinc of 3h as activationary time 1.5s, maximum service life Silver-colored reserve cell diaphragm.

Application is adopted the technical scheme that the modified cellulose hydrate-vinylon composite diaphragm paper of the present invention in the battery:

A kind of modified cellulose hydrate-vinylon composite diaphragm paper is applied in the battery, its main feature is that: modified water chemical fibre Tie up main diaphragm of the element-vinylon composite diaphragm paper as zinc-silver reserve battery, with modification cellulose hydrate-vinylon it is compound every Film paper bag covers zinc load, coats oxidation silver positive electrode with nylon yarn.

The advantages and positive effects of the present invention are:

Using due to using the present invention in modified cellulose hydrate-vinylon composite diaphragm Preparation Method made of paper and battery Completely new technical solution, compared with prior art, zinc-silver reserve battery diaphragm of the present invention overcomes the deficiencies in the prior art, energy There is provided activationary time 1.5s, maximum service life is greater than the zinc-silver reserve battery diaphragm of 3h.

Specific embodiment

In order to further understand the content, features and effects of the present invention, the following examples are hereby given, and it is described in detail It is as follows: