CN107046119B

CN107046119B - AGM separator capable of dissolving out colloid and application thereof

Info

Publication number: CN107046119B
Application number: CN201710045576.3A
Authority: CN
Inventors: 徐翠云; 李翔; 刘欣; 汪程红
Original assignee: NAYU NANO NEW MATERIALS Co Ltd JIANGXI CHINA
Current assignee: Shangrao Annatuo New Materials Co ltd
Priority date: 2017-01-22
Filing date: 2017-01-22
Publication date: 2020-01-21
Anticipated expiration: 2037-01-22
Also published as: CN107046119A

Abstract

The invention discloses an AGM separator capable of dissolving out colloid, which comprises 74-95% by mass of glass fiber, 0-8% by mass of organic fiber, 2-25% by mass of nano silicon dioxide and 0-5% by mass of functional auxiliary agent; the nano silicon dioxide has the particle size of 1.5-10 nm and the specific surface area of 680-1100 square meters per gram. The invention prepares the AGM separator which can dissolve colloid by adding the nano silicon oxide with small particle size and high specific surface area. The accumulator using the separator has charge-discharge cycle not less than 10 times, the dissolved nano-silica content not less than 50%, and the dissolved nano-silica gradually forms gel, thus forming the all-solid colloid accumulator. The invention opens up a new colloid storage battery manufacturing mode, avoids the glue adding process of the lead-acid storage battery, and solves the problems of difficult glue adding, nonuniform formation in the storage battery and the like of the traditional lead-acid storage battery.

Description

AGM separator capable of dissolving out colloid and application thereof

Technical Field

The invention belongs to the field of storage batteries, and particularly relates to an AGM (absorptive glass mat) separator capable of dissolving out colloid and application thereof.

Background

The lead-acid storage battery is a secondary battery with the highest technical maturity, the optimal use safety and the best cycle utilization rate, and occupies more than 72 percent of market share in various storage battery markets all over the world. Lead-acid storage batteries are widely applied to a plurality of fields such as electric bicycle and motorcycle batteries, automobile starting batteries, novel start-stop batteries, wind power photovoltaic energy storage batteries, communication base stations, data center standby power supplies, high-speed rail locomotive power supply systems and the like, and in order to meet industry requirements, the industry is developed at an accelerated rate of 20% in output in recent years.

In the manufacturing process of domestic lead-acid storage batteries, glass fiber separators always occupy absolute market share. After 2000 years, storage battery manufacturers grafted colloidal batteries on glass fiber separator storage batteries, added imported gas-phase silica or silica sol into electrolyte to gelatinize the electrolyte, and combined the AGM separator and the colloidal technology to improve the performance of the batteries.

As an improvement on the common lead-acid storage battery with liquid electrolyte, the colloid electrolyte replaces the sulfuric acid electrolyte, and the safety, the storage capacity, the discharge performance, the service life and the like of the common lead-acid storage battery are improved. In particular, gel batteries have the following advantages over lead-acid batteries with liquid electrolyte: the high-voltage power supply has the advantages of good use reliability in a deep-cycle discharge state, relatively long cycle life, strong overcharge resistance, wide working temperature range, low self-discharge rate, capability of being placed in any direction, good shock resistance, safe use and the like. Therefore, the gel battery is the development direction of the lead-acid storage battery industry.

The colloid battery can be put into use after being subjected to a formation process. The lead-acid storage battery has two chemical compositions of internal chemical composition and external chemical composition. The internal formation process is to cut and dry battery plates and then directly assemble the battery plates into a battery, and form the battery internally. The external formation is to finish the formation of the polar plate in a formation tank. Because the polar plate for the externally formed storage battery needs to be subjected to tank formation, water washing and drying in advance, the energy consumption is high, the environmental pollution is large, and the production of the externally formed lead-acid storage battery is completely forbidden in China in 2013.

Although the gel battery has a series of advantages, the difficulty in adding the gel and the nonuniform internal formation of the gel battery are always difficult problems in the industry. The root cause of the difficult glue adding and the uneven inner formation of the gel battery is caused by the glue adding process.

At present, the gel adding process of a gel battery generally comprises the steps of fully mixing dilute sulfuric acid with a certain proportion with silicon dioxide colloid, adding a storage battery, and achieving a gel state through an internal formation process; namely, the colloid and the dilute sulfuric acid are mixed uniformly in advance, and the colloid electrolyte is poured by an acid adding machine.

The internalized gel battery is formed inside the battery, and is easy to generate heat in the formation process. In the process of adding the gel into the internalized battery, the dilute sulfuric acid electrolyte reacts violently with active substances in the green plate to release a large amount of heat, the heat is accumulated, the heat cannot be released quickly in a short time, the temperature rises sharply, and the gel gelling time is shortened, so that the gel is accumulated in an area near a cluster in a concentrated manner. In the process of filling the colloid, the colloid forming gel is separated from acid under the filtering action of the partition plate, and part of the acid is blocked above the partition plate and cannot enter the battery, so that the insufficient amount of the acid added into the battery is easily caused, and the capacity and the service life of the battery are seriously influenced.

Due to the fact that the gel adding of the gel battery is difficult, the adding amount of electrolyte is insufficient, and the acid is distributed in the partition plate unevenly, the formation of the gel battery is uneven and incomplete. Generally speaking, the internal formation of the gel battery is not thorough enough, the capacity is decayed quickly, and the discharge capacity and the cycle service life are both inferior to those of the external gel battery.

Disclosure of Invention

Aiming at the defects or improvement requirements of the prior art, the invention aims to provide an AGM separator capable of dissolving colloid and an application thereof, wherein the AGM separator capable of dissolving colloid is prepared by adding 1.5-10 nm of silica with specific surface area of 680-1100 square meters per gram of nano-silica into the existing glass fiber separator. In the invention, in the production process of the AGM separator, a colloid material, namely nano silicon oxide with small particle size and high specific surface area is added; after the storage battery adopting the separator is subjected to container formation and charge-discharge circulation, the nano silicon oxide in the AGM separator is slowly released to form nano monodisperse transparent jelly-like colloid. The nano silicon oxide has small particle size, high specific surface area, more surface hydroxyl groups and high surface activity, and is tightly combined with the glass fiber through the action of the surface hydroxyl groups. The AGM separator which can dissolve out the colloid after the drying process has small primary particle diameter of the nano silicon oxide in the AGM separator, the primary particle diameter is only 1.5-10 nm, and the apparent particle diameter of the aggregation structure is large. The particles with large apparent particle size of the aggregation structure can ensure the structure of the separator, and cannot be quickly dissolved out under acidic conditions and charging conditions; the primary particle diameter of the nano silicon oxide is small, and the nano silicon oxide has certain conductivity less than 20 nm. In the process of repeated charge and discharge circulation of a storage battery adopting the separator, the nano silicon oxide with small primary particle size attached to the AGM separator is slowly released under the action of repeated expansion and contraction of a polar plate, the action of hydrogen and oxygen disturbance in the process of charge and discharge and the action of an electric field, and when the nano silicon oxide reaches a certain concentration, the released nano silicon oxide gradually forms nano monodisperse transparent jelly-like colloid under an acidic condition; after the accumulator using the separator is charged and discharged for 10 times, the elution amount of the nano silicon oxide is more than or equal to 50 percent, and the all-solid-state colloid accumulator is formed. The nanometer silicon oxide is uniformly distributed on the AGM separator, and the nanometer silicon oxide which is slowly dissolved out forms a uniform and stable three-dimensional network structure under the acidic condition, is in a nanometer monodisperse transparent jelly shape, and has the effect which is far superior to that of white aggregated emulsion colloid of a storage battery which is filled with nanometer silicon oxide colloid in sulfuric acid electrolyte. The AGM separator capable of dissolving out the colloid opens up a new colloid storage battery manufacturing scheme, avoids a glue adding process of a lead-acid storage battery, and solves the industrial problems of difficult glue adding, nonuniform formation in the storage battery and the like of the traditional lead-acid storage battery.

In order to achieve the above object, according to one aspect of the present invention, there is provided an AGM separator from which a colloid can be dissolved, the AGM separator comprising 74 to 95% by mass of glass fibers, 0 to 8% by mass of organic fibers, 2 to 25% by mass of nano silica, and 0 to 5% by mass of a functional additive; preferably, the particle size of the nano silicon dioxide is 1.5-10 nm, and the specific surface area is 680-1100 square meters per gram.

In a further preferred aspect of the present invention, the colloid-dissolvable AGM separator is configured such that, when a battery using the colloid-dissolvable AGM separator is subjected to a charge/discharge cycle, the nano silica in the colloid-dissolvable AGM separator is dissolved out to form a colloid; preferably, when the charge-discharge cycle of the storage battery adopting the AGM separator capable of dissolving colloid is more than or equal to 10 times, the quantity of dissolved nano silicon oxide in the AGM separator capable of dissolving colloid accounts for more than or equal to 50 percent of the total quantity of nano silicon dioxide.

As a further preferable mode of the invention, the mass percentage of the functional auxiliary agent is 0.8-3%.

As a further preferred of the present invention, the functional assistant includes at least one of a dispersant, a retention aid and a drainage aid.

As a further preferred option of the invention, the dispersant is one or more of sodium hexametaphosphate, potassium pyrophosphate, sodium alginate, sodium carboxymethylcellulose, polyethylene glycol and cetyl trimethyl ammonium bromide; the retention aid is one or more of alum, polyaluminium chloride, bentonite, modified starch, polyethyleneimine, polyethylene oxide, chitosan, carboxymethyl cellulose and polyacrylamide; the filter aid is one or more of diatomite, cationic starch, polyamide and polyacrylamide.

According to another aspect of the present invention, there is provided a use of the above-described gel-dissolvable AGM separator in a secondary battery.

According to still another aspect of the present invention, there is provided a secondary battery using the above-described gel-dissolvable AGM separator as a separator.

In a further preferred embodiment of the present invention, the secondary battery is a secondary battery using sulfuric acid as an electrolyte; preferably, the specific gravity of the sulfuric acid is 1.05-1.28 g/mL.

As a further preferred aspect of the present invention, the nano silica in the colloid-dissolvable AGM separator dissolves out to form a colloid when the battery is subjected to a charge-discharge cycle; preferably, when the charge-discharge cycle of the storage battery is more than or equal to 10 times, the amount of the dissolved nano silicon oxide in the AGM separator capable of dissolving colloid accounts for more than or equal to 50% of the total amount of the nano silicon dioxide.

According to the AGM separator capable of dissolving out the colloid, the storage battery adopting the separator has the charge-discharge cycle of more than or equal to 10 times, the dissolving-out amount of the nano silicon oxide is more than or equal to 50 percent, and the dissolved-out nano silicon oxide gradually forms nano monodisperse transparent jelly-like gel, namely the all-solid colloid storage battery is formed; the accumulator can adopt pure sulfuric acid solution as electrolyte, and the specific gravity of the sulfuric acid can be 1.05-1.28 g/mL.

According to the invention, the traditional colloid materials, namely gas phase nano-silica and silica sol, are replaced by the improved colloid materials, namely nano-silica with the particle size of 1.5-10 nm and the specific surface area of 680-1100 square meters per gram. The nano silicon oxide has the advantages of small particle size, high specific surface area, higher activity and rich internal network structure.

The nano silicon oxide has high activity and high surface hydroxyl content, and has certain binding force with glass fiber; other kinds of colloidal materials, such as fumed silica or silica sol, have large particle size, small specific surface area and poor surface activity, can only be used as fillers in fibers, and when the colloidal materials are added into an AGM separator, the separator has serious powder falling, and cannot adapt to mechanical production.

The nano silicon oxide has the particle size of 1.5-10 nm and abundant surface hydroxyl groups. The AGM separator which can dissolve out the colloid after the drying process has small primary particle diameter of the nano silicon oxide in the AGM separator, the primary particle diameter is only 1.5-10 nm, and the apparent particle diameter of the aggregation structure is large. The particles with large apparent particle size of the aggregation structure can ensure the structure of the separator, and cannot be quickly dissolved out under acidic conditions and charging conditions; the primary particle diameter of the nano silicon oxide is small, and the nano silicon oxide has certain conductivity less than 20 nm. In the process of repeated charge and discharge circulation of a storage battery adopting the separator, the nano silicon oxide with small primary particle size attached to the AGM separator is slowly released under the action of repeated expansion and contraction of a polar plate, the action of hydrogen and oxygen disturbance in the process of charge and discharge and the action of an electric field, and when the nano silicon oxide reaches a certain concentration, the released nano silicon oxide gradually forms nano monodisperse transparent jelly-like colloid under an acidic condition; after the accumulator using the separator is charged and discharged for 10 times, the elution amount of the nano silicon oxide is more than or equal to 50 percent, and the all-solid-state colloid accumulator is formed.

The nano silicon oxide has small primary particle size, rich surface hydroxyl, strong activity and excellent performance, is uniformly distributed on the AGM clapboard, and slowly released nano silicon oxide forms a uniform and stable three-dimensional network structure in a nano monodisperse transparent jelly shape under an acidic condition. The storage battery adopting the separator has the defects of few surface hydroxyl groups, insufficient activity, large primary particle size, serious agglomeration and the like, and even if a small amount of fumed silica or silica sol is added into the AGM separator, the storage battery adopting the separator is easy to form a white aggregation state in the cycle of repeated charge and discharge, and a monodisperse transparent colloid cannot be dissolved out.

According to the invention, nano silicon oxide with small particle size and high specific surface area is added into the AGM separator in advance, and part of the nano silicon oxide is dissolved out to form colloid in the process of charging and discharging of a storage battery adopting the separator; the storage battery adopting the separator can be internalized only by adding dilute sulfuric acid with a certain proportion, and no additional filling colloid is needed. The dissolved nano silicon oxide can form uniform and transparent colloid with a three-dimensional network structure, and the effect of the dissolved nano silicon oxide is far superior to that of white aggregated milky colloid of a storage battery filled with nano silicon oxide colloid in sulfuric acid electrolyte. In the prior art, the colloid and the dilute sulfuric acid are often required to be uniformly mixed in advance, and the colloid electrolyte is poured by an acid adding machine. The process of mixing the colloid and the dilute sulfuric acid in advance brings negative effects to the colloid adding process and the internal formation effect of the battery. In the formation process of the first container formation colloid battery, the dilute sulfuric acid electrolyte reacts violently with active substances in a green plate to release a large amount of heat, the heat is accumulated, the heat cannot be released quickly in a short time, and the temperature rises sharply to shorten the colloid gelling time, so that the gel is accumulated in an area near a cluster in a concentrated manner. In the process of filling the colloid, the colloid forming gel is separated from acid under the filtering action of the partition plate, and part of the acid is blocked above the partition plate and cannot enter the battery, so that the insufficient amount of the acid added into the battery is easily caused, and the capacity and the service life of the battery are seriously influenced; secondly, because the gel adding of the gel battery is difficult, the adding amount of the electrolyte is insufficient, and the acid is unevenly distributed in the partition plate, the formation of the gel battery is uneven and incomplete.

The nano silicon oxide is uniformly distributed on the AGM separator, and the colloid of the storage battery adopting the separator is slowly dissolved out in the charge-discharge cycle process. Because no colloid needs to be additionally poured, the phenomenon of blocking the clusters can not occur, enough dilute sulfuric acid can be added into the storage battery, and the phenomenon of acid shortage of the storage battery can not occur. The nano silicon oxide is uniformly distributed and dissolved out on the AGM separator, and the electrolyte layering phenomenon is effectively improved, so that the internal formation of the storage battery is uniform.

According to the AGM separator capable of dissolving out the colloid, the storage battery adopting the separator does not need additional glue adding, a new colloid storage battery manufacturing scheme is developed, the glue adding process of the lead-acid storage battery is omitted, and the industrial problems that the traditional lead-acid storage battery is difficult to add the glue, the storage battery is not uniform in formation and the like are solved.

In the invention, the storage battery adopting the separator has the charge-discharge cycle times of more than or equal to 10 times and the elution amount of the nano silicon oxide of more than or equal to 50 percent. The dissolution of the nano silicon oxide on the separator of the accumulator adopting the separator is a slow dynamic process. The AGM separator which can dissolve out the colloid after the drying process has small primary particle diameter of the nano silicon oxide in the AGM separator, the primary particle diameter is only 1.5-10 nm, and the apparent particle diameter of the aggregation structure is large. The nano silicon oxide and the glass fiber have certain binding force, and meanwhile, the nano silicon oxide primary particles combined with the glass fiber have certain conductive capacity, and the nano silicon oxide primary particles are slowly dissociated from the glass fiber under the action of an external force of repeated contraction and expansion of the polar plate, an acting force of hydrogen and oxygen disturbance in the charging and discharging processes and an electric field. During the initial charge-discharge cycle of the storage battery, the elution amount of the nano-silica on the partition board is very small, and through continuous charge-discharge cycle, the disturbing acting force of hydrogen and oxygen and repeated contraction and expansion of the polar plate, the dissociated nano-silica is gradually increased to gradually form colloid under the action of acid.

The nano-silica in the invention can be added during pulping (namely, the nano-silica is added into the glass fiber slurry during preparation of the glass fiber slurry), or can be added after a wet separator is formed (namely, a process of applying the nano-silica on the surface of the separator slurry after negative pressure pumping and dehydration is adopted). Because the hydroxyl function of the surface of the nano silicon oxide with small particle size and high specific surface area is tightly combined with the glass fiber, the adhesive force of the nano silicon oxide and the fiber can be enhanced, and the using amount of the functional auxiliary agent in the preparation process can be effectively reduced.

In the invention, the nano silicon dioxide with small particle size and high specific surface area can not be dehydrated and dried, and the water content of the nano silicon dioxide with small particle size and high specific surface area reaches 87 percent, thus the nano silicon dioxide is represented as a solid state and has strong water retention capacity. Pulping and dispersing by using a high-speed emulsification homogenizer to prepare the emulsion for standby.

The AGM separator capable of dissolving out the colloid in the present invention may be used in combination with other processes, and the dehydration may be, for example, vacuum negative pressure low pressure dehydration treatment or vacuum strong dehydration treatment.

The AGM separator capable of dissolving out the colloid is further assembled to obtain the storage battery, other structures and components (such as a polar plate and the like) of the storage battery are the same as those of the valve-regulated AGM lead-acid storage battery, the acid adding process can adopt a conventional process for adding acid, and the internal formation process can adopt a conventional formation process.

Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:

(1) the AGM separator capable of dissolving out the colloid is prepared by adopting nano silicon dioxide with excellent performance, small particle size and high specific surface area to replace the traditional colloid materials, namely fumed silica and silica sol. The storage battery adopting the separator has the charge-discharge cycle of more than or equal to 10 times, the dissolved nano-silicon oxide content is more than or equal to 50 percent, and the dissolved nano-silicon oxide gradually forms nano-monodisperse transparent jelly-like gel, namely the all-solid colloid storage battery is formed.

(2) The nanometer silicon oxide is added into the AGM separator in advance, and the dissolved nanometer silicon oxide can form a uniform and transparent colloid with a three-dimensional network structure, and the effect of the colloid is far superior to that of a white aggregated milky colloid of a storage battery filled with the nanometer silicon oxide colloid added into a sulfuric acid electrolyte. The storage battery adopting the separator does not need to additionally add colloid, the colloid adding process of the colloid battery is omitted, and a new colloid storage battery manufacturing scheme is developed.

(3) The problems of difficult glue adding, nonuniform formation in the storage battery and the like of the traditional lead-acid storage battery are solved, the capacity decline of the battery is slowed down, and the cycle service life of the battery is prolonged.

Drawings

FIG. 1 is a schematic diagram of a method of making a colloid-dissolvable AGM separator according to the present invention;

FIG. 2 is a battery anatomy diagram obtained by dissecting a battery after 10 cycles of charging and discharging by adding acid to a separator with 2% of nano-silica according to a conventional process (corresponding to example 1);

FIG. 3 is a battery anatomy diagram obtained by dissecting a battery after 10 cycles of charging and discharging by adding acid to a separator with 16% of nano-silica according to a conventional process; it is evident from the figure that there is gel on the upper part of the pole group, on the side and inside the partition (corresponding to example 4);

FIG. 4 is a battery anatomy diagram obtained by dissecting a battery after 10 cycles of charging and discharging by adding acid to a separator with 20% of nano-silica according to a conventional process; it is clear from the figure that there is gel on the top, side and inside of the separator, and the gel is more as the amount of nano silica is increased (corresponding to example 5).

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

The AGM separator capable of dissolving out the colloid comprises the following components in percentage by mass: 74-95% of glass fiber, 0-8% of organic fiber for improving the performance of the partition board, 2-25% of nano silicon dioxide and 0-5% (preferably 0.8-3%) of functional auxiliary agent;

the particle size of the nanometer silicon dioxide of the AGM clapboard capable of dissolving colloid is 1.5-10 nm, and the specific surface area is 680-1100 square meters per gram;

wherein, the organic fiber and the functional auxiliary agent can be added or not added.

The functional assistant is at least one of dispersant with dispersing function, retention aid with retention function and filter aid with filter aid function.

As shown in fig. 1, the method for producing an AGM separator in which a colloid is eluted in the present invention may employ two production methods.

The first preparation method can comprise the following steps:

(1) preparing nano silicon oxide water dispersion liquid: adding a proper amount of water into an emulsifying machine, adding 0.25-2.60% of a dispersing agent, and pulping; adding 2-25% of nano silicon dioxide, and pulping at high speed to obtain a nano silicon oxide water dispersion liquid;

in the process, 0.25-2.60% of dispersing agent is added, so that the nano silicon oxide exists in the fiber mixed slurry in a monodispersed mode and the fiber is dispersed;

in the process, an emulsifying machine is adopted for high-speed pulping, which is determined by small particle size and easy agglomeration of the nano silicon oxide, and the high-speed pulping is beneficial to dispersing the nano silicon oxide;

(2) material preparation and pulping: adding a proper amount of water into a beater, sequentially adding the nano silicon oxide water dispersion liquid, the retention aid and the filter aid in the step (1) to 0.2-2.55%, and beating; adjusting the pH value, adding 74-95% of glass fiber, and pulping; adding 0-8% of organic fiber for improving the performance of the partition board, and pulping;

in the process, 0.2-2.55% of retention aid is added, the retention aid is beneficial to the retention of glass fibers and nano silicon oxide, and the loss of the glass fibers and the nano silicon oxide in the preparation process of the partition board is reduced;

in the process, 0.2-2.55% of filter aid is added, so that the filter aid is beneficial to reducing the filtration resistance, and the filter residue is prevented from being accumulated too densely, so that the filtration is carried out smoothly;

(3) size mixing and deslagging: adding water for dilution, adjusting the pH value, and then carrying out slag removal treatment;

(4) molding: performing negative pressure suction filtration dehydration on the slurry obtained in the step (3), and controlling the final water content of the partition plate to be 65-68%;

(5) drying: drying the wet partition plate at 130-150 ℃ for 3-5 minutes, and then drying at 180 ℃ for 10-20 minutes; in the process, the mixture is dried at low temperature for 3-5 minutes, so that the shaping of an AGM separator capable of dissolving out the colloid is facilitated, and then the mixture is dried at high temperature to remove redundant moisture;

(6) and (6) coiling and cutting.

The second preparation method may include the steps of:

(1) preparing nano silicon oxide water dispersion liquid: adding a proper amount of water into an emulsifying machine, adding 0.25-2.60% of a dispersing agent, and pulping; adding 2-25% of nano silicon dioxide, and pulping at a high speed to prepare a nano silicon oxide water dispersion liquid;

in the process, 0.25-2.60% of dispersing agent is added, so that the existence of nano silicon oxide in a monodispersed form and the dispersion of the nano silicon oxide are facilitated;

(2) material preparation and pulping: adding a proper amount of water into a pulping machine, sequentially adding 0.2-2.55% of retention aid and 0.2-2.55% of filter aid, and pulping; adjusting the pH value, adding 74-95% of glass fiber, and pulping; adding 0-8% of organic fiber for improving the performance of the partition board, and pulping;

in the process, 0.2-2.55% of retention aid is added, the retention aid is added to assist the retention of the glass fiber, and the loss of the glass fiber in the preparation process of the partition board is reduced;

(4) one-step forming: carrying out negative pressure suction filtration dehydration on the slurry obtained in the step (3), and controlling the water content to be 70-85%; in the process, the high water content of the partition board is kept at 70-85%, and the partition board is of a fluffy structure, so that the nano silicon oxide applied subsequently is attached to the surface of the glass fiber partition board and permeates into the glass fiber partition board;

(5) applying silicon dioxide on the surface of the separator: applying the nano-silica aqueous dispersion in the step (1) on the surface of a wet partition plate; the addition of the nano silicon oxide is ensured to be 2-25% by adjusting the running speed of the paper machine and the concentration of the nano silicon oxide aqueous solution or the spraying speed thereof;

(6) secondary molding: carrying out negative pressure suction filtration dehydration on the middle partition plate in the step (5), and controlling the final water content of the partition plate to be 65-68%;

(7) drying: drying the wet partition plate at 130-150 ℃ for 3-5 minutes to shape the partition plate, drying at 180 ℃ for 5-8 minutes, and removing excessive water in the partition plate;

(8) and (6) coiling and cutting.

The following are specific examples:

example 1

In this embodiment, the components and contents of the AGM separator from which the colloid can be dissolved are as follows by mass percent: 87% of glass fiber, 8% of polyester fiber, 2% of nano silicon dioxide and 3% of functional auxiliary agent.

When the method is implemented, the method comprises the following steps:

(1) preparing nano silicon oxide water dispersion liquid: adding a proper amount of water into an emulsifying machine, adding 0.25 percent of potassium pyrophosphate, and pulping; adding 2% of nano silicon dioxide, and pulping at high speed to obtain nano silicon oxide water dispersion liquid;

(2) material preparation and pulping: adding a proper amount of water into a pulping machine, sequentially adding the nano silicon oxide water dispersion liquid, the alum 2.55% and the cationic starch 0.2% in the step (1), and pulping; adjusting the pH value, adding 87 percent of glass fiber, and pulping; adding 8% of polyester fiber and pulping;

(5) drying: drying the wet partition plate at 130-150 ℃ for 3-5 minutes, and then drying at 180 ℃ for 10-20 minutes;

(6) coiling, cutting, assembling the storage battery and carrying out an internal formation process on the storage battery.

The storage battery under the process is not subjected to charge-discharge cycle, and the dissolution amount of the nano silicon oxide is 0.32% by determination; after the storage battery is subjected to charge-discharge cycles for 3 times, the dissolution amount of the nano silicon oxide is 12.65 percent through measurement; after the storage battery is subjected to charge-discharge cycles for 6 times, the dissolution amount of the nano silicon oxide is 22.41 percent through measurement; after the storage battery is subjected to 10 charge-discharge cycles, the dissolution amount of the nano silicon oxide is measured to be 50.87%.

Example 2

In this embodiment, the components and contents of the AGM separator from which the colloid can be dissolved are as follows by mass percent: 95% of glass fiber, 4.2% of nano silicon dioxide and 0.8% of functional auxiliary agent.

When the method is implemented, the method comprises the following steps:

(1) preparing nano silicon oxide water dispersion liquid: adding a proper amount of water into an emulsifying machine, adding 0.25 percent of polyethylene glycol, and pulping; adding 4.2% of nano silicon dioxide, and pulping at high speed to obtain nano silicon oxide water dispersion liquid;

(2) material preparation and pulping: adding a proper amount of water into a beater, sequentially adding the nano silicon oxide water dispersion liquid, the chitosan, the carboxymethyl cellulose and the polyamide in the step (1) to pulp, wherein the nano silicon oxide water dispersion liquid, the carboxymethyl cellulose and the polyamide are 0.1 percent and 0.35 percent; adjusting the pH value, adding glass fiber to 95 percent, and pulping;

The storage battery under the process is not subjected to charge-discharge cycle, and the dissolution amount of the nano silicon oxide is 0.45% by determination; after the storage battery is subjected to charge-discharge cycles for 3 times, the dissolution amount of the nano silicon oxide is 11.98 percent through measurement; after the storage battery is subjected to charge-discharge cycles for 6 times, the dissolution amount of the nano silicon oxide is 23.4 percent through measurement; after the storage battery is subjected to 10 charge-discharge cycles, the dissolution amount of the nano silicon oxide is determined to be 51.45%.

Example 3

In this embodiment, the components and contents of the AGM separator from which the colloid can be dissolved are as follows by mass percent: 80% of glass fiber, 7% of polyethylene fiber, 10% of nano silicon dioxide and 3% of functional auxiliary agent.

When the method is implemented, the method comprises the following steps:

(1) preparing nano silicon oxide water dispersion liquid: adding a proper amount of water into an emulsifying machine, adding 0.1% of sodium hexametaphosphate, 0.1% of sodium carboxymethyl cellulose and 0.05% of polyethylene glycol, and pulping; adding 10% of nano silicon dioxide, and pulping at high speed to obtain nano silicon oxide water dispersion liquid;

(2) material preparation and pulping: adding a proper amount of water into a pulping machine, sequentially adding the nano silicon oxide water dispersion liquid, the polyaluminium chloride 0.2% and the polyacrylamide 2.55% in the step (1), and pulping; adjusting the pH value, adding 80 percent of glass fiber, and pulping; adding 7% of polyethylene fiber and pulping;

The storage battery under the process is not subjected to charge-discharge cycle, and the dissolution amount of the nano silicon oxide is 0.39% by determination; after the storage battery is subjected to charge-discharge cycles for 3 times, the dissolution amount of the nano silicon oxide is 13.01 percent through measurement; after the storage battery is subjected to charge-discharge cycles for 6 times, the dissolution amount of the nano silicon oxide is 23.87 percent through measurement; after the storage battery is subjected to 10 charge-discharge cycles, the dissolution amount of the nano silicon oxide is determined to be 52.44%.

Example 4

In this embodiment, the components and contents of the AGM separator from which the colloid can be dissolved are as follows by mass percent: 74% of glass fiber, 7% of polyethylene fiber, 16% of nano silicon dioxide and 3% of functional auxiliary agent.

When the method is implemented, the method comprises the following steps:

(1) preparing nano silicon oxide water dispersion liquid: adding a proper amount of water into an emulsifying machine, adding 2 percent of sodium hexametaphosphate and 0.6 percent of sodium carboxymethyl cellulose, and pulping; adding 16% of nano silicon dioxide, and pulping at high speed to prepare nano silicon oxide water dispersion liquid;

(2) material preparation and pulping: adding a proper amount of water into a beater, sequentially adding 0.05% of polyaluminium chloride, 0.1% of alum, 0.05% of polyethylene oxide and 0.2% of diatomite, and beating; adjusting the pH value, adding 74 percent of glass fiber, and pulping; adding 7% of polyethylene fiber and pulping;

(4) one-step forming: carrying out negative pressure suction filtration dehydration on the slurry obtained in the step (3), and controlling the water content to be 70-85%;

(5) applying silicon dioxide on the surface of the separator: applying the nano-silica aqueous dispersion in the step (1) on the surface of a wet partition plate; the addition of the nano silicon oxide is ensured to be 16 percent by adjusting the running speed of the paper machine and the concentration of the nano silicon oxide aqueous solution or the spraying speed thereof;

(7) drying: drying the wet partition plate at 130-150 ℃ for 3-5 minutes, and then drying at 180 ℃ for 10-20 minutes;

(8) coiling, cutting, assembling the storage battery and carrying out an internal formation process on the storage battery.

The storage battery under the process is not subjected to charge-discharge cycle, and the dissolution amount of the nano silicon oxide is 0.51 percent by determination; after the storage battery is subjected to charge-discharge cycles for 3 times, the dissolution amount of the nano silicon oxide is 12.17 percent through measurement; after the storage battery is subjected to charge-discharge cycles for 6 times, the dissolution amount of the nano silicon oxide is 20.98 percent through measurement; after the storage battery is subjected to 10 charge-discharge cycles, the dissolution amount of the nano silicon oxide is measured to be 50.14%.

Example 5

In this embodiment, the components and contents of the AGM separator from which the colloid can be dissolved are as follows by mass percent: 77.5 percent of glass fiber, 20 percent of nano silicon dioxide and 2.5 percent of functional auxiliary agent.

When the method is implemented, the method comprises the following steps:

(1) preparing nano silicon oxide water dispersion liquid: adding a proper amount of water into an emulsifying machine, adding 1% of sodium alginate, and pulping; adding 20% of nano silicon dioxide, and pulping at high speed to prepare nano silicon oxide water dispersion liquid;

(2) material preparation and pulping: adding a proper amount of water into a pulping machine, sequentially adding 1% of bentonite, 0.3% of diatomite, 0.1% of cationic starch and 0.1% of polyacrylamide, and pulping; adjusting the pH value, adding 77.5 percent of glass fiber, and pulping;

(5) applying silicon dioxide on the surface of the separator: applying the nano-silica aqueous dispersion in the step (1) on the surface of a wet partition plate; the addition of the nano silicon oxide is ensured to be 20 percent by adjusting the running speed of the paper machine and the concentration of the nano silicon oxide aqueous solution or the spraying speed thereof;

The storage battery under the process is not subjected to charge-discharge cycle, and the dissolution amount of the nano silicon oxide is 0.62% by determination; after the storage battery is subjected to charge-discharge cycles for 3 times, the dissolution amount of the nano silicon oxide is 14.28 percent through measurement; after the storage battery is subjected to charge-discharge cycles for 6 times, the dissolution amount of the nano silicon oxide is 24.59 percent through measurement; after the storage battery is subjected to 10 charge-discharge cycles, the dissolution amount of the nano silicon oxide is 53.41 percent.

Example 6

In this embodiment, the components and contents of the AGM separator from which the colloid can be dissolved are as follows by mass percent: 74.1 percent of glass fiber, 25 percent of nano silicon dioxide and 0.9 percent of functional auxiliary agent.

When the method is implemented, the method comprises the following steps:

(1) preparing nano silicon oxide water dispersion liquid: adding a proper amount of water into an emulsifying machine, adding 0.5 percent of hexadecyl trimethyl ammonium bromide, and pulping; adding 25% of nano silicon dioxide, and pulping at high speed to prepare nano silicon oxide water dispersion liquid;

(2) material preparation and pulping: adding a proper amount of water into a pulping machine, sequentially adding 0.1% of modified starch, 0.1% of polyethyleneimine and 0.2% of polyacrylamide, and pulping; adjusting the pH value, adding 74.1 percent of glass fiber, and pulping;

(5) applying silicon dioxide on the surface of the separator: applying the nano-silica aqueous dispersion in the step (1) on the surface of a wet partition plate; the addition of the nano silicon oxide is ensured to be 25 percent by adjusting the running speed of the paper machine and the concentration of the nano silicon oxide aqueous solution or the spraying speed thereof;

The storage battery under the process is not subjected to charge-discharge cycle, and the dissolution amount of the nano silicon oxide is 0.59 percent by determination; after the storage battery is subjected to charge-discharge cycles for 3 times, the dissolution amount of the nano silicon oxide is 15.08 percent through measurement; after the storage battery is subjected to charge-discharge cycles for 6 times, the dissolution amount of the nano silicon oxide is 23.97 percent through measurement; after the storage battery is subjected to 10 charge-discharge cycles, the dissolution amount of the nano silicon oxide is determined to be 52.18%.

Example 7

In this embodiment, the components and contents of the AGM separator from which the colloid can be dissolved are as follows by mass percent: 75% of glass fiber and 25% of nano silicon dioxide.

When the method is implemented, the method comprises the following steps:

(1) preparing nano silicon oxide water dispersion liquid: adding a proper amount of water into an emulsifying machine, then adding 25% of nano silicon dioxide, and pulping at a high speed to prepare nano silicon oxide water dispersion;

(2) material preparation and pulping: adding a proper amount of water into a beater, adding 75% of glass fiber, and beating;

The storage battery under the process is not subjected to charge-discharge cycle, and the dissolution amount of the nano silicon oxide is 0.5% by determination; after the storage battery is subjected to charge-discharge cycles for 3 times, the dissolution amount of the nano silicon oxide is 14.08 percent through measurement; after the storage battery is subjected to charge-discharge cycles for 6 times, the dissolution amount of the nano silicon oxide is 21.97 percent through measurement; after the storage battery is subjected to 10 charge-discharge cycles, the dissolution amount of the nano silicon oxide is determined to be 51.08%.

Example 8

In this embodiment, the components and contents of the AGM separator from which the colloid can be dissolved are as follows by mass percent: 90% of glass fiber, 5% of nano silicon dioxide and 5% of functional auxiliary agent.

When the method is implemented, the method comprises the following steps:

(1) preparing nano silicon oxide water dispersion liquid: adding a proper amount of water into an emulsifying machine, adding 2 percent of sodium hexametaphosphate and 0.6 percent of sodium carboxymethyl cellulose, and pulping; adding 5 percent of nano silicon dioxide, and pulping at high speed to prepare nano silicon oxide water dispersion liquid;

(2) material preparation and pulping: adding a proper amount of water into a pulping machine, sequentially adding 0.2% of polyaluminium chloride and 2.2% of polyacrylamide, and pulping; adjusting the pH value, adding 90 percent of glass fiber, and pulping;

(5) applying silicon dioxide on the surface of the separator: applying the nano-silica aqueous dispersion in the step (1) on the surface of a wet partition plate; the addition of the nano silicon oxide is ensured to be 5 percent by adjusting the running speed of the paper machine and the concentration of the nano silicon oxide aqueous solution or the spraying speed thereof;

The storage battery under the process is not subjected to charge-discharge cycle, and the dissolution amount of the nano silicon oxide is 0.46 percent by measurement; after the storage battery is subjected to charge-discharge cycles for 3 times, the dissolution amount of the nano silicon oxide is 12.08 percent through measurement; after the storage battery is subjected to charge-discharge cycles for 6 times, the dissolution amount of the nano silicon oxide is 23.5 percent through measurement; after the storage battery is subjected to 10 charge-discharge cycles, the dissolution amount of the nano silicon oxide is determined to be 51.48%.

The organic fiber in the invention refers to fiber with organic material, including terylene, acrylon, chinlon, polypropylene fiber and high performance fiber, including aramid fiber, ultra-high molecular weight polyethylene fiber (UHMWPE fiber), poly-p-phenylene benzobisoxazole fiber (PBO fiber), poly-p-benzimidazole fiber (PBI fiber), poly-p-phenylene pyridobisimidazole fiber (M5 fiber), polyimide fiber (PI fiber) and so on.

The dispersing agent in the invention is one or more of dispersing aids such as sodium hexametaphosphate, potassium pyrophosphate, sodium alginate, sodium carboxymethyl cellulose, polyethylene glycol, cetyl trimethyl ammonium bromide and the like; the retention aid is one or more of aids with retention effect, such as alum, polyaluminium chloride, bentonite, modified starch, polyethyleneimine, polyethylene oxide, chitosan, carboxymethyl cellulose, polyacrylamide and the like; the filter aid is one or more of auxiliary agents with filter aid effects such as diatomite, cationic starch, polyamide and polyacrylamide.

It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims

1. Use of an AGM separator from which a gel can be dissolved in a battery; the AGM separator capable of dissolving out the colloid is characterized by comprising 74-95% by mass of glass fiber, 0-8% by mass of organic fiber, 2-25% by mass of nano silicon dioxide and 0-5% by mass of functional auxiliary agent; the particle size of the nano silicon dioxide is 1.5-10 nm, and the specific surface area is 680-1100 square meters per gram;

when the colloid-dissolvable AGM separator is specifically applied, the colloid-dissolvable AGM separator is arranged in a storage battery as a separator to obtain the storage battery adopting the colloid-dissolvable AGM separator, and then the storage battery is subjected to internalization and charge-discharge circulation to dissolve nano silicon dioxide in the colloid-dissolvable AGM separator to form colloid; when the charge-discharge cycle of a storage battery adopting the AGM separator capable of dissolving out the colloid is more than or equal to 10 times, the proportion of the dissolved-out nano silicon dioxide in the AGM separator capable of dissolving out the colloid accounts for more than or equal to 50 percent of the total amount of the nano silicon dioxide;

the functional assistant comprises at least one of a dispersant, a retention aid and a filter aid.

2. The application of claim 1, wherein the mass percent of the functional auxiliary agent is 0.8-3%.

3. The use of claim 1, wherein the dispersant is one or more of sodium hexametaphosphate, potassium pyrophosphate, sodium alginate, sodium carboxymethylcellulose, polyethylene glycol, and cetyltrimethylammonium bromide; the retention aid is one or more of alum, polyaluminium chloride, bentonite, modified starch, polyethyleneimine, polyethylene oxide, chitosan, carboxymethyl cellulose and polyacrylamide; the filter aid is one or more of diatomite, cationic starch, polyamide and polyacrylamide.

4. A storage battery using an AGM separator capable of dissolving colloid as a separator is characterized in that the AGM separator capable of dissolving colloid comprises 74-95% by mass of glass fiber, 0-8% by mass of organic fiber, 2-25% by mass of nano silicon dioxide and 0-5% by mass of functional auxiliary agent; the particle size of the nano silicon dioxide is 1.5-10 nm, and the specific surface area is 680-1100 square meters per gram;

the storage battery adopting the AGM separator capable of dissolving out the colloid as the separator is subjected to internalization and charge-discharge cyclic treatment, so that the nano silicon dioxide in the AGM separator capable of dissolving out the colloid is dissolved out to form colloid; when the charge-discharge cycle of the storage battery is more than or equal to 10 times, the quantity of the dissolved nano silicon dioxide in the AGM separator capable of dissolving the colloid accounts for more than or equal to 50 percent of the total quantity of the nano silicon dioxide;

5. The battery of claim 4, wherein the battery is sulfuric acid as an electrolyte.

6. The battery of claim 5, wherein said sulfuric acid has a specific gravity of 1.05-1.28 g/mL.