CN115632172A

CN115632172A - Lead-carbon battery colloidal electrolyte and preparation method and perfusion method thereof

Info

Publication number: CN115632172A
Application number: CN202211327654.6A
Authority: CN
Inventors: 邵永刚; 杨少华; 方亮; 汪笃达; 何湖民
Original assignee: Anhui Accord Science And Technology Co ltd
Current assignee: Anhui Accord Science And Technology Co ltd
Priority date: 2022-10-27
Filing date: 2022-10-27
Publication date: 2023-01-20
Anticipated expiration: 2042-10-27
Also published as: CN115632172B

Abstract

The invention belongs to the field of lead-carbon batteries, and particularly relates to a lead-carbon battery colloidal electrolyte which comprises, by weight, 0.5-7% of silicon dioxide, 30-45% of sulfuric acid, 0.3-1% of phosphoric acid, 0.3-1% of boric acid, 1-2% of an additive, 1-2% of a stabilizer and the balance of deionized water; the additive comprises 0.15-0.4% of polyvinyl alcohol, 0.3-0.8% of glycerol and 0.55-0.8% of glycol; the stabilizer is a metal-organic coordination polymer formed by manganese sulfate and 3,5-bis (pyridine-4-yl) -4-amino-1,2,4-triazole. The invention has the beneficial effects that: the colloidal electrolyte has the advantages of high stability, large capacity, high cycling stability, no bleeding, no acid leakage and the like through a scientific formula design and a preparation method, the service life and the use safety performance of the colloidal storage battery are effectively improved, and the capacity retention rate can still reach 95% after the colloidal storage battery is cycled for 200 times.

Description

Lead-carbon battery colloidal electrolyte and preparation method and perfusion method thereof

Technical Field

The invention belongs to the field of lead-carbon batteries, and particularly relates to a lead-carbon battery colloidal electrolyte, and a preparation method and a perfusion method thereof.

Background

The lead-carbon battery is a capacitive lead-acid battery, is a technology evolved from the traditional lead-acid battery, and can obviously prolong the service life of the lead-acid battery by adding activated carbon into the negative electrode of the lead-acid battery. The lead-carbon battery is a novel super battery, and integrates a lead-acid battery and a super capacitor: the advantages of instantaneous high-capacity charging of the super capacitor and the specific energy of the lead-acid battery are exerted, and the lead-acid battery has good charging and discharging performance. That is, the lead-acid battery can be fully charged in 90 minutes (if the lead-acid battery is charged and discharged, the service life is only less than 30 times). And because the carbon (graphene) is added, the negative electrode sulfation phenomenon is prevented, a factor of the failure of the traditional battery is improved, and the service life of the battery is prolonged.

The colloid lead-acid accumulator is an improvement on the ordinary lead-acid accumulator with liquid electrolyte, and the colloid electrolyte is used to replace sulfuric acid electrolyte, so that it has improved safety, capacity, discharge performance and service life. The gel lead-acid storage battery adopts gel electrolyte, no free liquid exists in the gel lead-acid storage battery, the electrolyte has large capacity and heat capacity and strong heat dissipation capacity under the same volume, and the phenomenon of thermal runaway of a common storage battery can be avoided; the electrolyte concentration is low, and the corrosion effect on the polar plate is weak; the concentration is uniform, and the electrolyte layering phenomenon does not exist.

For example, a chinese patent publication No. CN101763950B discloses a colloidal lead-carbon supercapacitor, in which an activated carbon cathode (activated carbon is used as an active substance) is used as a cathode, a lead anode (PbO 2 is used as an active substance) is used as an anode, PVC-SiO2 is used as a separator, and a colloidal electrolyte is used as an electrolyte. The components of the colloidal electrolyte comprise 2-8 wt.% of fumed silica, 1-3.5 wt.% of polyacrylamide, 0.5-2 wt.% of phosphoric acid, 81-92 wt.% of sulfuric acid and 2-11 wt.% of deionized water, and the sum of the components is 100%. The active carbon negative electrode material is prepared by mixing conductive carbon black, active carbon, CMC, a binder and water. The active carbon negative electrode material comprises the following components in percentage by weight: 0.1-5 wt.% of conductive carbon black, 80-90 wt.% of active carbon, 0.1-5 wt.% of CMC, 0.1-5 wt.% of binder (such as LA 132), and the balance of water. The anode material is formed by mixing lead powder, short fibers, conductive carbon black, dilute sulfuric acid and water. The positive electrode material lead plaster comprises the following components: 80-90 wt.% of lead powder, 0.01-0.5 wt.% of short fiber, 0.1-5 wt.% of conductive carbon black, 1-5 wt.% of dilute sulfuric acid (1.1-1.4 g/cm < 3 >), and the balance of water. For another example, a chinese patent publication No. CN106025381B discloses a lead-carbon colloidal battery colloidal electrolyte formula and a preparation method thereof, wherein the lead-carbon colloidal battery colloidal electrolyte formula comprises the following components in parts by mass: 90-98 parts of dilute sulfuric acid with the density of 1.20-1.28g/ml at 25 ℃; 0.3-2.5 parts of silicon dioxide with the particle size of 1-9 nm; 0.5-3 parts of an additive; 2.5-10 parts of deionized water; wherein the additive is a mixture of polytetrafluoroethylene, phosphoric acid and sodium sulfate. The preparation method of the colloidal electrolyte of the lead-carbon colloidal battery comprises the following steps: s1, putting deionized water into a container, adding an additive, then adding silicon dioxide, and stirring for 5-10min to obtain a colloidal electrolyte mother liquor; s2, diluting concentrated sulfuric acid with deionized water to obtain 1.20-1.28g/ml dilute sulfuric acid with the density of 25 ℃, cooling to below 15 ℃, mixing the dilute sulfuric acid with the colloidal electrolyte mother liquor obtained in the step S1, and stirring for 5-15S to obtain a colloidal electrolyte product.

However, the electrolyte of the current colloid lead-acid storage battery is mainly composed of a certain amount of silica sol or gas phase SiO ₂ A colloid formed by dispersing in sulfuric acid. The electrolyte prepared by the former has the defects of poor stability, poor thixotropy, easy hydration, easy cracking and the like; the latter is costly and the electrolyte performance is largely determined by the gas phase SiO ₂ And the degree of utilization of the colloid is filledThe injected storage battery is easy to have the problems of low battery capacity, large internal resistance, easy hydration of colloid and the like.

In addition, a key and difficult point in the production of lead carbon gel batteries is the impregnation of the gel electrolyte. Currently, there are two methods available for silica sol-infused batteries. Firstly, adding acid and then adding gel, namely adding a certain volume of high-density sulfuric acid electrolyte into the battery, then adding a silicon solution with a certain silicon dioxide content, and fully mixing the acid and the gel through a certain charging and discharging process to achieve a gel state. The second method, mixing and pouring, is to mix high-density sulfuric acid and silicon solution, then add them into the battery, and carry out certain charge and discharge treatment to get the gel state. The first process is simple and can ensure the battery capacity, but the defect is obvious, and the silicon dioxide in the gel is unevenly distributed; the second process has the obvious advantages of uniform distribution of silicon dioxide and sulfuric acid in the gel, uniform electrolyte filling, low self-discharge rate and predicted battery life longer than that of the battery manufactured by the prior acid adding process. However, the second process has the technical problem that the filling difficulty is high due to the fact that the gel is refilled, and the process points to be considered are many, such as how to exhaust gas in the electrolyte filling process, how to ensure the battery capacity, and the like.

Disclosure of Invention

In order to solve the problems, the invention provides a lead-carbon battery colloidal electrolyte and a preparation method thereof, the colloidal electrolyte has the advantages of high stability, large capacity, high cycling stability, no water precipitation, no acid leakage and the like, and meanwhile, the invention also provides a perfusion method of the colloidal electrolyte, so that the gas discharge in the battery and the battery capacity can be ensured in the electrolyte perfusion process, the technical problem existing in the mixed perfusion is solved, and the production quality and the service life of the lead-carbon colloidal battery are improved.

The invention provides the following technical scheme:

the invention aims to provide a lead-carbon battery colloidal electrolyte, which comprises 0.5-7% of silicon dioxide, 30-45% of sulfuric acid, 0.3-1% of phosphoric acid, 0.3-1% of boric acid, 1-2% of an additive, 1-2% of a stabilizer and the balance of deionized water in percentage by weight;

the additive comprises 0.15-0.4% of polyvinyl alcohol, 0.3-0.8% of glycerol and 0.55-0.8% of glycol;

the stabilizer is a metal-organic coordination polymer formed by manganese sulfate and 3,5-bi (pyridine-4-yl) -4-amino-1,2,4-triazole;

the 3,5-bis (pyridin-4-yl) -4-amino-1,2,4-triazole has the following structure:

preferably, the preparation method of the metal-organic ligand is as follows:

adding manganese sulfate and 3,5-bis (pyridine-4-yl) -4-amino-1,2,4-triazole into a reaction kettle, adding isopropanol and deionized water, carrying out sealed ultrasonic oscillation for 0.5-1h, reacting for 1-2 days at 150-170 ℃, cooling to 20-30 ℃, and filtering to obtain a tan cubic crystal, namely the metal-organic coordination polymer.

Preferably, the molar ratio of the manganese sulfate to the 3,5-bis (pyridin-4-yl) -4-amino-1,2,4-triazole is (2-4): 1.

preferably, the silicon dioxide is nano silicon dioxide, and the particle size of the nano silicon dioxide is 20-30nm.

Another object of the present invention is to provide a method for preparing a colloidal electrolyte, comprising the steps of:

s1, putting deionized water into a container, then adding silicon dioxide, and performing rotary shearing at the speed of 1000-3000r/min for 5-10min to obtain a colloidal electrolyte mother liquor;

s2, pretreating the sulfuric acid at a low temperature of 0 ℃ for 20-40min, and adding phosphoric acid and boric acid into the sulfuric acid to obtain mixed acid;

s3, preparing an additive solution from the additive and deionized water;

s4, preparing a stabilizer solution from a stabilizer and deionized water;

and S5, mixing the mother liquor, the mixed acid, the additive solution and the stabilizer solution, and shearing for 10-15min at the rotation speed of 1000-3000r/min to obtain the colloidal electrolyte.

The invention also provides a method for pouring colloid electrolyte, which comprises a shell and an end cover, wherein a positive plate, a negative plate and a partition plate are arranged in the shell at intervals, a communicating valve is arranged on the end cover, a first channel communicated with the bottom of an inner cavity of the shell is arranged in one side wall of the shell, a second channel communicated with the first channel is arranged on the end cover, a glue injection channel is arranged in the end cover, glue injection holes communicated with the inner cavity of the shell are arranged at intervals at the inner end of the glue injection channel, the communicating valve is provided with four interfaces, the first interface is communicated with the second interface, the third interface is communicated with the fourth interface, the second interface is communicated with the outer end of the glue injection channel, and the third interface is communicated with the second channel; the related perfusion device comprises an upper rotary table and a lower rotary table which rotate synchronously, a plurality of battery seats for mounting the colloid battery are radially and uniformly distributed on the upper rotary table, a glue injection cylinder is vertically arranged at the center of the upper rotary table, a glue injection port for connecting with a first interface of the colloid battery is correspondingly arranged at the bottom of the glue injection cylinder, a sealing plug is arranged in the glue injection cylinder in a sliding manner, a screw rod is connected to the sealing plug, a transmission gear is rotatably arranged at the top of the glue injection cylinder, an internal thread matched with the screw rod is arranged at the center of the transmission gear, the transmission gear is meshed with a driving gear, the driving gear is connected with a driving motor, a glue storage box and a glue return box are arranged on the lower rotary table, a glue adding box is arranged on the upper rotary table, a conveying pump is arranged in the glue storage box, the glue storage box is communicated with the glue adding box, the glue adding box is communicated with the root of the glue injection cylinder, the glue return box is connected with a fourth interface of a communication valve, the glue return box is a closed box, and a vacuum pump is arranged on the glue return box;

the perfusion method comprises the following steps:

s1, pouring colloidal electrolyte into a glue storage box, conveying the colloid into a glue adding box by a conveying pump, and filling the glue adding box with the colloidal mixed electrolyte all the time;

s2, a plurality of colloid batteries are installed in each battery seat of the upper rotary table, one side wall with a first channel on each colloid battery is placed upwards, and the colloid batteries are filled according to the capacity of each colloid battery, the glue filling amount of the glue filling cylinder each time and each colloid batteryThe overflow of the colloid required by the pool is calculated, and the frequency V of the glue injection required by the glue injection barrel is calculated _Cartridge n _{Number of times} ＝(V _Pool +V _{For treating} )N _{Number of pools} Wherein V is _Cartridge N is the glue injection quantity of the glue injection cylinder at each time _{Number of times} Number of times of injection of glue required for a cartridge of glue, V _Pool For the capacity of each gel cell, V _{For treating} Gel overflow, N, required for each gel cell _{Number of pools} The number of the colloid batteries which are injected with glue at one time;

s3, driving a motor to rotate, driving a transmission gear to rotate through a driving gear, driving a sealing plug to move upwards along an adhesive injection cylinder through a screw rod by the transmission gear, and injecting the colloid mixed electrolyte in the adhesive adding box into the adhesive injection cylinder;

s4, driving the motor to rotate reversely, gradually moving the sealing plug downwards, and injecting the colloid mixed electrolyte in the glue injection cylinder into each colloid battery;

s5, the upper rotary disc and the lower rotary disc rotate simultaneously, colloid mixed electrolyte in the colloid storage box is stirred to a certain degree, meanwhile, each colloid battery synchronously rotates along with the upper rotary disc, the colloid mixed electrolyte is filled to the bottom of each colloid battery under the action of centrifugal force, the inner cavity of each colloid battery is filled, air in the inner cavity of each colloid battery enters the colloid return box through the first channel and the second channel and is pumped away by the vacuum pump, meanwhile, after the colloid mixed electrolyte is filled in the inner cavity of each colloid battery, redundant colloid mixed electrolyte can enter the colloid return box through the first channel and the second channel, and a certain amount of colloid overflow is set to ensure that all gas remained in the colloid mixed electrolyte is discharged into the colloid return box;

s6, repeating the steps from S3 to S5 to finish the n times of glue injection required by the glue injection barrel;

and S7, taking down each colloid battery, and sealing and communicating the first interface and the fourth interface on the valve.

Preferably, a first electromagnetic valve is arranged between the glue adding box and the glue injection cylinder, a second electromagnetic valve is arranged at the glue injection port, when the sealing plug moves upwards, the first electromagnetic valve is opened, the second electromagnetic valve is closed, when the sealing plug moves downwards, the first electromagnetic valve is closed, and the second electromagnetic valve is opened.

Preferably, a communicating pipe is connected between the bottom of the glue storage tank and the bottom of the glue return tank.

The invention has the beneficial effects that:

1. the colloidal electrolyte has the advantages of high stability, large capacity, high cycling stability, no bleeding, no acid leakage and the like through a scientific formula design and a preparation method, the service life and the use safety performance of the colloidal storage battery are effectively improved, and the capacity retention rate can still reach 95% after the colloidal storage battery is cycled for 200 times.

2. By adding phosphoric acid and boric acid, the performance of the colloidal electrolyte is improved, the capacity of the colloidal battery is improved, and the cycle life is prolonged. The use of a proper amount of additives in the invention not only can make the gel network structure elastic, but also can properly reduce the dosage of silicon dioxide.

3. The metal-organic coordination polymer is used as a stabilizer, 3,5-bis (pyridine-4-yl) -4-amino-1,2,4-triazole is a polydentate ligand, has a multi-nitrogen heterocyclic structure, is easy to form intermolecular interaction such as pi-pi stacking and hydrogen bonding, and 3,5-bis (pyridine-4-yl) -4-amino-1,2,4-triazole and manganese sulfate form a rigid ligand bond angle which is relatively fixed, the distance between coordination teeth and the configuration of a group are not obviously changed, and the metal-organic coordination polymer can rotate but cannot bend during coordination, so that the metal-organic coordination polymer with a relatively large cavity and stability is more easily formed, a formed three-dimensional network structure is beneficial to improving the stability of an electrolyte, the dosage of silicon dioxide is greatly reduced, the influence of the silicon dioxide on the ionic conductivity is reduced, the metal-organic coordination polymer has high pores, high specific surface area and multiple pore channels inside, an excellent ion transfer channel exists, the ion transfer efficiency is improved, and the ion exchange performance of copper ions and the like is excellent. Therefore, lead ions in the lead-carbon battery can be adsorbed by the surface of electrolyte and can enter the interior of the electrolyte structure to generate an ion confinement, so that the uniform deposition and dispersion of the ions under the action of an electric field are ensured, and the electrochemical performance of the battery is finally improved.

4. Compared with the prior art, the invention has the advantages that during the filling process, the upper rotating disc and the lower rotating disc synchronously rotate, the colloid injected into the battery shell from the colloid injection cylinder on the upper rotating disc is under the filling force of the sealing plug, and the colloid is automatically thrown into the inner cavity of the battery shell under the centrifugal force to ensure the battery capacity, meanwhile, as the first channel and the second channel in the colloid battery are positioned above, the first channel and the second channel can not only discharge the air in the battery shell, but also ensure that the inner cavity of the battery shell is filled with the colloid, because the colloid can only enter the colloid return box from the first channel and the second channel after the inner cavity of the battery shell is filled with the colloid, in addition, in the process of filling, still designed the colloid overflow to every colloid battery, guarantee promptly from battery case's first passageway and second passageway backward flow to the glue incasement glue volume of returning, can ensure that the gas of sneaking into the colloid also discharges to returning the glue incasement along with it, in addition, the evacuation pump on returning the glue case except can extracting the gas in the battery case, can also inhale the bubble of sneaking into the colloid, and finally, the synchronous rotation of lower carousel, can also carry out stirring mixing action to a certain extent to the colloid mixed electrolyte of glue case and returning of storage, the delivery pump of glue incasement is guaranteed to be full of the colloid in the case that adds all the time, avoid the air sneak into, and simultaneously, be convenient for the colloid pours into in the injecting glue section of thick bamboo.

Drawings

FIG. 1 is a schematic structural diagram of a device for injecting a gel-mixed electrolyte according to an embodiment of the present invention;

fig. 2 is a partially enlarged view of a portion a in fig. 1.

Detailed Description

The present invention will be described in detail with reference to the following examples.

Unless otherwise specified, various raw material reagents used in the present invention are commercially available.

3,5-bis (pyridin-4-yl) -4-amino-1,2,4-triazole has the following structural formula:

preparation example 1

Preparation of the stabiliser (Metal-organic coordination Polymer)

Adding 6mol of manganese sulfate and 18mol of 3,5-bis (pyridine-4-yl) -4-amino-1,2,4-triazole into a reaction kettle, adding 6L of isopropanol and 2L of deionized water, sealing and ultrasonically oscillating for 1h, reacting at 160 ℃ for 1 day, cooling to 25 ℃, and filtering to obtain a tan cubic crystal, namely the metal-organic coordination polymer.

Example 1

The lead-carbon battery colloidal electrolyte comprises, by weight, 0.5% of silicon dioxide, 30% of sulfuric acid, 0.3% of phosphoric acid, 0.3% of boric acid, 0.15% of polyvinyl alcohol, 0.3% of glycerol, 0.55% of ethylene glycol, 1% of a metal-organic coordination polymer and the balance of deionized water.

The silicon dioxide is nano silicon dioxide, and the particle size of the nano silicon dioxide is 20nm.

Example 2

The present example is different from example 1 in that "the particle diameter of nano silica is 30nm", and the other points are exactly the same as example 1.

Example 3

This example is different from example 1 in "silica 4%", and is otherwise exactly the same as example 1.

Example 4

This example is different from example 1 in "7% silica", and is completely the same as example 1.

Example 5

The present example is different from example 1 in that "silica 7% and nano-silica having a particle size of 30nm" are completely the same as example 1.

Example 6

This example is different from example 1 in that "2% of a metal-organic complex polymer" is used, and the rest is completely the same as example 1.

Example 7

The lead-carbon battery colloidal electrolyte comprises 7% of silicon dioxide, 45% of sulfuric acid, 1% of phosphoric acid, 1% of boric acid, 0.4% of polyvinyl alcohol, 0.8% of glycerol, 0.8% of glycol, 2% of metal-organic coordination polymer and the balance of deionized water in percentage by weight.

Comparative example 1

This example is different from example 1 in "9% silica", and is identical to example 1 except for the point.

Comparative example 2

The present example is different from example 1 in that "the particle diameter of nano silica is 40nm", and the other points are exactly the same as example 1.

Comparative example 3

This example is different from example 1 in "0.5% of a metal-organic complex polymer", and is completely the same as example 1.

Comparative example 4

This example is different from example 1 in "3% of a metal-organic complex polymer", and is completely the same as example 1.

Example 8

A preparation method of a colloidal electrolyte comprises the following steps:

s1, putting deionized water into a container, then adding silicon dioxide, and shearing for 10min by rotating at 1500r/min to obtain a colloidal electrolyte mother solution;

s2, pretreating the sulfuric acid at the low temperature of 0 ℃ for 30min, and adding phosphoric acid and boric acid into the sulfuric acid to obtain mixed acid;

s3, preparing an additive solution from the additive and deionized water;

s4, preparing a stabilizer solution from a stabilizer and deionized water;

and S5, mixing the mother liquor, the mixed acid, the additive solution and the stabilizer solution, and shearing for 15min at the rotating speed of 1500r/min to obtain the colloidal electrolyte.

The formulations of examples 1-7 and comparative examples 1-4 were prepared as colloidal electrolytes and subjected to electrochemical testing as follows:

the negative electrode adopts an active carbon negative electrode (taking active carbon as the negative electrode)As active material), the positive electrode adopts lead positive electrode (made of PbO) ₂ As active substance), a separator of PVC-SiO is used ₂ And performing charge and discharge test in a constant current charge and discharge mode, wherein the current density range is 0.05-0.5A/g, and the voltage range is 1-1.8V.

TABLE 1 EXAMPLES 1-7, COMPARATIVE EXAMPLES 1-4 Electrical tests

As shown in Table 1, the specific capacity of the battery under 0.05A/g is not much different from that of the examples 1 to 7 and the comparative examples 1 to 4, and both the specific capacity and the comparative examples exceed 370mAh/g, wherein the specific capacity of the battery under the embodiment 6 with the best effect reaches 450mAh/g, and in the capacity retention rate test of 200 times of circulation under 0.5A/g, the effects of the examples 1 to 7 are obviously better than those of the comparative examples 1 to 4, and the capacity retention rate of the example 6 with the best effect reaches 95% after 200 times of circulation.

Example 9

A colloidal electrolyte perfusion method comprises the steps that a colloidal battery 6 comprises a shell 61 and an end cover 62, a positive plate, a negative plate and a partition plate are arranged in the shell 61 at intervals, a communication valve 63 is arranged on the end cover 62, a first channel 611 communicated with the bottom of an inner cavity of the shell 61 is arranged in one side wall of the shell 61, a second channel 621 communicated with the first channel 611 is arranged on the end cover 62, a glue injection channel 622 is arranged in the end cover 62, glue injection holes 623 communicated with the inner cavity of the shell 61 are arranged at intervals at the inner end of the glue injection channel 622, the communication valve 63 is provided with four interfaces, the first interface 631 is communicated with the second interface 632, the third interface 633 is communicated with the fourth interface 634, the second interface 632 is communicated with the outer end of the glue injection channel 622, and the third interface 633 is communicated with the second channel 621; the related perfusion device comprises an upper rotary disc 11 and a lower rotary disc 12 which rotate synchronously, a plurality of battery seats for mounting the colloid battery 6 are radially and uniformly distributed on the upper rotary disc 11, a glue injection cylinder 3 is vertically arranged at the center of the upper rotary disc 11, a glue injection port 31 for connecting with a first port 631 of the colloid battery 6 is correspondingly arranged at the bottom of the glue injection cylinder 3, a sealing plug 4 is arranged in the glue injection cylinder 3 in a sliding manner, a screw rod 41 is connected onto the sealing plug 4, a transmission gear 5 is rotatably arranged at the top of the glue injection cylinder 3, an internal thread matched with the screw rod 41 is arranged at the center of the transmission gear 5, the transmission gear 5 is meshed with a driving gear 51, the driving gear 51 is connected with a driving motor 52, a glue storage box 21 and a glue return box 23 are arranged on the lower rotary disc 12, a glue adding box 22 is arranged on the upper rotary disc 11, a conveying pump 211 is arranged in the glue storage box 21, the glue storage box 21 is communicated with the glue adding box 22, the glue adding box 22 is communicated with the root 634 of the glue adding box 3, the glue adding box 23 is communicated with a fourth port of a communication valve 63, the glue return box 23 is a closed box, and a vacuum pump 231 is arranged on the glue return box 23;

the perfusion method comprises the following steps:

s1, pouring colloidal electrolyte into a glue storage box 21, conveying the glue into a glue adding box 22 by a conveying pump 211, and filling the glue adding box 22 with the colloidal mixed electrolyte all the time;

s2, a plurality of colloid batteries 6 are installed in each battery seat of the upper rotary table 11, one side wall with a first channel 611 on each colloid battery 6 is placed upwards, and the glue injection times and V needed by the glue injection barrel 3 are calculated according to the capacity of each colloid battery 6, the glue injection amount of the glue injection barrel 3 at each time and the colloid overflow amount needed by each colloid battery 6 _Cartridge n _{Number of times} ＝(V _Pool +V _{For treating} )N _{Number of pools} Wherein V is _Cartridge For each injection quantity, n, of the injection tube 3 _{Number of times} Number of times of dispensing required for the dispensing cartridge 3, V _Pool For the capacity, V, of each gel cell 6 _{For treating} The required gel overflow, N, for each gel battery 6 _{Number of pools} The number of the colloid batteries which are injected with glue at one time;

s3, driving the motor 52 to rotate, driving the transmission gear 5 to rotate through the driving gear 51, driving the sealing plug 4 to move upwards along the glue injection barrel 3 through the transmission gear 5 through the screw rod 41, and injecting the colloid mixed electrolyte in the glue adding box 22 into the glue injection barrel 3;

s4, the driving motor 52 rotates reversely, the sealing plug 4 descends gradually, and the colloid mixed electrolyte in the glue injection barrel 3 is injected into each colloid battery 6;

s5, the upper turntable 11 and the lower turntable 12 rotate simultaneously, the colloid mixed electrolyte in the colloid storage box 21 is stirred to a certain degree, meanwhile, each colloid battery 6 rotates synchronously along with the upper turntable 11, under the action of centrifugal force, the colloid mixed electrolyte fills the bottom of the colloid battery 6 to fill the inner cavity of the whole colloid battery 6, air in the inner cavity of the colloid battery 6 enters the colloid return box 23 through the first channel 611 and the second channel 621 and is pumped away by the vacuum pump 231, meanwhile, after the colloid mixed electrolyte fills the inner cavity of the whole colloid battery 6, redundant colloid mixed electrolyte enters the colloid return box 23 from the first channel 611 and the second channel 621, and through setting a certain amount of colloid flow, the gas remained in the colloid mixed electrolyte is ensured to be all discharged back into the colloid return box 23;

s6, repeating the steps from S3 to S5 to finish the n times of glue injection required by the glue injection barrel 3;

s7, each gel battery 6 is removed, and the first port 631 and the fourth port 634 of the communication valve 63 are sealed.

A first electromagnetic valve is arranged between the glue adding box 22 and the glue injection barrel 3, a second electromagnetic valve is arranged at the glue injection port 31, when the sealing plug 4 moves upwards, the first electromagnetic valve is opened, the second electromagnetic valve is closed, when the sealing plug 4 moves downwards, the first electromagnetic valve is closed, and the second electromagnetic valve is opened.

And a communicating pipe is connected between the bottoms of the glue storage tank 21 and the glue return tank 23. In this way, after the vacuum pump 231 pumps out the air mixed in the glue returning box 23, the glue without air bubbles can be returned to the glue storage box 21 again, and the glue can be recycled.

In summary, during the filling process, the upper rotating disc 11 and the lower rotating disc 12 rotate synchronously, on the upper rotating disc 11, the colloid injected into the battery case 61 from the colloid injecting cylinder 3 is not only acted by the filling force of the sealing plug 4, but also thrown into the inner cavity of the battery case 61 under the centrifugal action force, so as to ensure the battery capacity, meanwhile, because the first channel 611 and the second channel 621 in the colloid battery 6 are located above, in this way, the first channel 611 and the second channel 621 can not only exhaust the air inside the battery case 6, but also ensure that the inner cavity of the battery case 61 is filled with the colloid, because the colloid can enter the colloid returning box 23 from the first channel 611 and the second channel 621 only after the inner cavity of the battery case 61 is filled with the colloid, in addition, during the filling process, still designed the colloid overflow volume to every colloid battery 6, guarantee promptly from battery case 61's first passageway 611 and second passageway 621 backward flow to the glue volume in returning gluey case 23, can ensure that the gas in sneaking into the colloid also discharges to returning gluey case 23 in along with, in addition, return the vacuum pump 231 on gluey case 23 except can extracting the gas in the battery case 61, can also suck out the bubble of sneaking into the colloid, finally, the synchronous revolution of lower carousel 12, can also carry out stirring mixing action to a certain extent to the colloid mixed electrolyte in glue storage box 21 and the glue return case 23, delivery pump 211 in the glue storage box 21 ensures to be full of the colloid in the gluey case 22, avoid the air to sneak into, simultaneously, be convenient for the colloid pours into in the injecting glue section of thick bamboo 3 all the time.

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

1. The lead-carbon battery colloidal electrolyte is characterized by comprising 0.5-7% of silicon dioxide, 30-45% of sulfuric acid, 0.3-1% of phosphoric acid, 0.3-1% of boric acid, 1-2% of an additive, 1-2% of a stabilizer and the balance of deionized water in percentage by weight;

the stabilizer is a metal-organic coordination polymer formed by manganese sulfate and 3,5-bis (pyridine-4-yl) -4-amino-1,2,4-triazole;

the 3,5-bis (pyridin-4-yl) -4-amino-1,2,4-triazole has the following structure:

2. the lead-carbon battery colloidal electrolyte of claim 1, wherein the metal-organic ligand is prepared by the following method:

manganese sulfate and 3,5-bis (pyridine-4-yl) -4-amino-1,2,4-triazole are added into a reaction kettle, isopropanol and deionized water are added, the mixture is subjected to sealed ultrasonic oscillation for 0.5 to 1h, the mixture reacts for 1 to 2 days at the temperature of 150 to 170 ℃, the temperature is reduced to 20 to 30 ℃, and brown cubelike crystals are obtained through filtration, namely the metal-organic coordination polymer.

3. The lead-carbon battery colloidal electrolyte as defined in claim 2, wherein the molar ratio of manganese sulfate, 3,5-bis (pyridin-4-yl) -4-amino-1,2,4-triazole is (2-4): 1.

4. the lead-carbon battery colloidal electrolyte according to claim 1, wherein the silica is nano silica, and the particle size of the nano silica is 20-30nm.

5. A method for preparing a colloidal electrolyte as defined in any one of claims 1 to 4, comprising the steps of:

s3, preparing an additive solution from the additive and deionized water;

s4, preparing a stabilizer solution from a stabilizer and deionized water;

and S5, mixing the mother liquor, the mixed acid, the additive solution and the stabilizer solution, and performing rotary shearing at the speed of 1000-3000r/min for 10-15min to obtain the colloidal electrolyte.

6. A colloidal electrolyte perfusion method as in any one of claims 1-4, wherein the colloidal battery (6) comprises a casing (61) and an end cover (62), the positive plate, the negative plate and the separator are arranged in the casing (61) at intervals, the end cover (62) is provided with a communication valve (63), a first channel (611) communicated with the bottom of the inner cavity of the casing (61) is arranged in one side wall of the casing (61), the end cover (62) is provided with a second channel (621) communicated with the first channel (611), the end cover (62) is provided with a glue injection channel (622), the inner end of the glue injection channel (622) is provided with a glue injection hole (623) communicated with the inner cavity of the casing (61) at intervals, the communication valve (63) is provided with four ports, the first port (631) is communicated with the second port (632), the third port (633) is communicated with the fourth port (634), the second port (632) is communicated with the outer end of the glue injection channel (622), and the third port (633) is communicated with the second channel (633); the related perfusion device comprises an upper rotary disc (11) and a lower rotary disc (12) which rotate synchronously, a plurality of battery seats used for installing colloid batteries (6) are radially and uniformly distributed on the upper rotary disc (11), a glue injection barrel (3) is vertically arranged at the center of the upper rotary disc (11), the bottom of the glue injection barrel (3) is correspondingly provided with a glue injection port (31) used for being connected with a first interface (631) of the colloid batteries (6), a sealing plug (4) is arranged in the glue injection barrel (3) in a sliding manner, a screw rod (41) is connected onto the sealing plug (4), a transmission gear (5) is rotatably arranged at the top of the glue injection barrel (3), the center of the transmission gear (5) is provided with an internal thread matched with the screw rod (41), the transmission gear (5) is meshed with a driving gear (51), the driving gear (51) is connected with a driving motor (52), a glue storage box (21) and a glue return box (23) are arranged on the lower rotary disc (12), a glue adding box (22) is arranged on the upper rotary disc (11), a conveying pump (211) is arranged in the glue storage box (21), the glue adding box is communicated with the glue adding box (21), a glue adding valve (634), and the glue adding box (23) is communicated with a fourth glue adding box (23) and communicated with the glue adding port (63), a vacuum pump (231) is arranged on the glue returning box (23); the perfusion method comprises the following steps:

s1, pouring colloidal electrolyte into a glue storage box (21), conveying the colloid into a glue adding box (22) by a conveying pump (211), and filling the glue adding box (22) with the colloid mixed electrolyte all the time;

s2, mixingA plurality of colloid batteries (6) are arranged in each battery seat of the upper turntable (11), one side wall of each colloid battery (6) with a first channel (611) is placed upwards, and the glue injection frequency and the glue injection V required by the glue injection barrel (3) are calculated according to the capacity of each colloid battery (6), the glue injection amount of each glue injection barrel (3) and the glue overflow amount required by each colloid battery (6) _Cartridge n _{Number of times} ＝(V _Pool +V _{For treating} )N _{Number of pools} Wherein, V _Cartridge N is the amount of glue injected into the glue injection cylinder (3) each time _{Number of times} Number of times of injection of glue required for the cartridge (3) of glue injection, V _Pool Is the capacity, V, of each gel cell (6) _{For treating} The required gel overflow, N, for each gel cell (6) _{Number of pools} The number of the colloid batteries which are injected with glue at one time;

s3, a driving motor (52) rotates, a driving gear (51) drives a transmission gear (5) to rotate, the transmission gear (5) drives a sealing plug (4) to move upwards along a glue injection barrel (3) through a screw rod (41), and a colloid mixed electrolyte in a glue adding box (22) is injected into the glue injection barrel (3);

s4, the driving motor (52) rotates reversely, the sealing plug (4) descends gradually, and the colloid mixed electrolyte in the glue injection barrel (3) is injected into each colloid battery (6);

s5, the upper rotary disc (11) and the lower rotary disc (12) rotate simultaneously, colloid mixed electrolyte in the colloid storage box (21) is stirred to a certain degree, meanwhile, each colloid battery (6) synchronously rotates along with the upper rotary disc (11), the colloid mixed electrolyte is filled into the bottom of each colloid battery (6) under the action of centrifugal force to fill the inner cavity of the whole colloid battery (6), air in the inner cavity of each colloid battery (6) enters the colloid return box (23) through the first channel (611) and the second channel (621), and is pumped away by the vacuum pump (231), meanwhile, after the colloid mixed electrolyte fills the inner cavity of the whole colloid battery (6), redundant colloid mixed electrolyte can enter the colloid return box (23) from the first channel (611) and the second channel (621), and a certain amount of colloid overflow is set, so that all gas remained in the mixed electrolyte is discharged into the colloid return box (23);

s6, repeating the steps from S3 to S5 to finish the n times of glue injection required by the glue injection barrel (3);

and S7, removing each colloid battery (6), and sealing the first interface (631) and the fourth interface (634) on the communication valve (63).

7. A method for pouring a colloidal electrolyte according to claim 6, wherein: a first electromagnetic valve is arranged between the glue adding box (22) and the glue injection barrel (3), a second electromagnetic valve is arranged at the glue injection port (31), the first electromagnetic valve is opened when the sealing plug (4) moves upwards, the second electromagnetic valve is closed, and the first electromagnetic valve is closed and the second electromagnetic valve is opened when the sealing plug (4) moves downwards.

8. A method for pouring a colloidal electrolyte according to claim 6, wherein: and a communicating pipe is connected between the bottoms of the glue storage tank (21) and the glue return tank (23).