CN110364774B

CN110364774B - Storage battery energy storage and regeneration method for large energy storage station

Info

Publication number: CN110364774B
Application number: CN201910666255.4A
Authority: CN
Inventors: 娄志林; 颜爱国; 颜玲轩; 娄里夫
Original assignee: Xiangtan Zhongchuang Electric Co ltd
Current assignee: Xiangtan Zhongchuang Electric Co ltd
Priority date: 2019-07-23
Filing date: 2019-07-23
Publication date: 2022-02-11
Anticipated expiration: 2039-07-23
Also published as: CN110364774A

Abstract

The invention discloses a storage battery energy storage and regeneration method for a large energy storage station. On the structure of a common liquid lead-acid battery, lead electrodes of the storage battery are arranged on a detachable polar plate bracket, and the side walls of two sides of the detachable polar plate bracket are provided with shallow grooves adaptive to the thickness of a battery polar plate, so that positive and negative polar plates are inserted into the shallow grooves in a crossed manner, and the positive and negative polar plates are fixed; then putting the whole bracket into a battery shell, and adding electrolyte to form the whole structure of the battery; and the battery is repaired by two-stage repair. The invention provides an economical battery energy storage and regeneration recycling technology based on the traditional liquid lead-acid battery, so that the service life of the battery is close to infinite cycle, the regeneration cost does not exceed 5 percent of the cost of newly purchasing a new battery after the service life of the battery is over, no waste is discharged, the environmental protection pressure after the battery is scrapped is avoided, the application cost of the storage battery in a large-scale energy storage power station can be obviously reduced, and the economical efficiency and the environmental protection property are obviously improved.

Description

Storage battery energy storage and regeneration method for large energy storage station

Technical Field

The invention relates to the field of battery energy storage, in particular to a storage battery energy storage and regeneration method for a large energy storage station.

Background

The technology of the storage battery has been from the invention to the present for over 200 years, from the common electrolyte lead-acid storage battery to the maintenance-free lead-acid storage battery, and then to the present lithium battery. The technology is improved more and more, the energy density is higher and higher, the allowable charging speed is higher and higher, the service life is longer and longer, but the improvement is limited, and the charging and discharging period of the best storage battery at present is improved from the first hundreds of times to no more than 2000 times. The limitation of service life means that the cost cannot be reduced. However, the energy structure of the existing power grid is mainly large thermal power plants in the past, and due to the requirements of environmental protection, one-time petrochemical resource exhaustion and ecological protection, gradual transition is required to be made to renewable energy mainly comprising wind power and photovoltaic, which are unstable and uncontrollable during power generation compared with thermal power, so that new requirements are provided for stable operation of the power grid, a large energy storage facility must be built to ensure stable operation of the power grid, and the limited service life of the existing storage battery technology, no matter what materials and processes are adopted, limits the application of the storage battery in power grid-level energy storage in cost.

Disclosure of Invention

The invention aims to provide a storage battery energy storage and regeneration method for a large-scale energy storage station.

The technical scheme of the invention is as follows:

a storage battery energy storage and regeneration method for a large energy storage station comprises the following steps:

(1) on the structure of a common liquid lead-acid battery, lead electrodes of the storage battery are arranged on a detachable polar plate bracket, and the side walls of two sides of the detachable polar plate bracket are provided with shallow grooves adaptive to the thickness of a battery polar plate, so that positive and negative polar plates are inserted into the shallow grooves in a crossed manner, and the positive and negative polar plates are fixed; therefore, the whole battery pole plate can be conveniently detached and moved, and the pole plate can be conveniently moved out for repairing after the performance of the battery pole plate is reduced or the service life of the battery pole plate is over;

(2) putting the support containing the positive and negative plates obtained in the step (1) into a battery shell integrally, and then adding electrolyte (dilute sulfuric acid) to form an integral structure of the battery;

(3) the restoration of battery polar plate, ordinary lead acid battery through several hundred to a thousand charge-discharge cycles, capacity reduces or even loses efficacy gradually, and its reason is that battery polar plate surface forms a lead sulfate coarse grain crystallization, has hindered the contact of electrolyte and polar plate, in order to restore the battery, needs to decompose this part lead sulfate, restores and divides the second grade to go on:

(a) first-stage repair: the battery pole plate to be repaired and the detachable pole plate support are integrally moved out of the battery tank and placed in a prepared repairing tank, distilled water or deionized pure water is injected into the repairing tank, an acid-resistant circulating pump is arranged at the edge of the repairing tank, and circulating water in the repairing tank flows through gaps among the pole plates; the volume of the repair groove is more than one time larger than that of the battery groove, and a detachable polar plate bracket containing a new polar plate or a cleaned lead sulfate polar plate is additionally arranged in the repair groove; the method comprises the following steps of (1) slightly dissolving lead sulfate in water (the temperature is 0.041 g/kg of water at 20 ℃), starting a circulating pump and a power supply for 0.2-1.5 hours to ensure that the lead sulfate on the surface of a polar plate is dissolved to be saturated, adding a pulse constant-current power supply to the positive electrode and the negative electrode of a new polar plate or a battery with a cleaned lead sulfate polar plate, controlling the pulse frequency to be 0.5-2000 Hz, the duty ratio to be 20-90%, controlling the average current to be 4-6% of the battery capacity, (for example, controlling the charging current to be 40-60A by a battery at 1000 ampere hours), controlling the open-circuit voltage of the pulse constant-current power supply to be 3-10 times of the battery voltage, and charging for 18-22 hours; during the charging process, lead ions dissolved in water obtain electrons on a new polar plate or a negative plate of the battery with a cleaned lead sulfate polar plate, the electrons become spongy pure lead, the electrons are lost on the positive plate, and the spongy pure lead is combined with oxygen ions in the water to generate lead dioxide; continuously reducing lead ions in water, reducing the concentration, continuously dissolving lead sulfate crystallized on a battery pole plate to be repaired, charging for 18-22 hours to basically dissolve the lead sulfate on the battery pole plate to be repaired, depositing lead dioxide on a charging position to recover the capacity of the lead dioxide to be more than 80% of the capacity of a primary battery, and if the white lead sulfate crystals on the surface are not obviously eliminated or cannot be recovered to more than 80% of the capacity by visual inspection, continuously prolonging the charging time (namely cleaning time), prolonging the charging time by more than one time, and not recovering to more than 80% of the capacity of the primary battery, adopting a secondary repairing method. The aim of separating the pole plate to be repaired from the charging pole plate is to prevent pure cathode lead and anode lead dioxide which are charged and deposited from covering the lead sulfate crystals which need to be cleaned, and to ensure that the lead sulfate crystals are fully contacted and dissolved with water. Because a large energy storage station has a large number of battery packs, the work can be continuously and circularly carried out. Most of lead ions in the electrolyte in the repair tank are collected by electrolysis, but residual lead ions and sulfate ions from dissolved lead sulfate are remained in the solution. If the water is discharged randomly, the environment can be seriously polluted. But the water can be recycled without discharging. The cost of the treatment is very low, which is basically the cost of one-time charging, and is less than 0.5 percent of the cost of a newly-invested battery;

(b) secondary repair: the one-time repair service cycle of a general lead-acid battery plate does not exceed one thousand charge-discharge cycles, namely 2-3 years, after 3-5 first-level repairs, the method can not recover more than 80% of the capacity of a new battery, the battery plate can be moved out and placed in a pure water tank to be soaked for 25-40 minutes to wash away residual sulfuric acid (the soaking water can also be used for replenishing water to the battery), then the battery plate is moved out and drained, the plate is completely detached from a bracket and placed in a crucible to be melted, and as the specific gravity of lead is 11.3, the melting point is 327 ℃, the melting point of lead sulfate is 1087 ℃ and the specific gravity is 6.2, when the crucible is higher than 327 ℃, the lead plate is melted, the lead sulfate forms scum, the scum is removed and collected, the melted lead water is cast into the plate again, and lead water can contain trace lead sulfate particles, but the service performance of the plate is not influenced, and the lead sulfate scum is sent to a professional smeltery to be recovered, the lost lead sulfate is continuously used after supplementing part of new lead and trace elements of the original polar plate in the same formula, so that the scrapping of the whole storage battery is avoided, the shell and the electrolyte are continuously reused, the cost for replacing the new battery is saved, a large amount of logistics and the commercial cost for recycling and selling the new battery are saved, and the environmental protection pressure caused by scrapping the whole battery is relieved. The cost for recasting the polar plate and supplementing a small amount of new lead is not more than 5 percent of that for resetting the new battery, the technical standard for resetting the new battery is achieved, a small amount of funds can be recovered by processing part of lead sulfate, and no waste is discharged in the whole process.

The invention has the beneficial effects that:

(1) the product of the invention is only suitable for large-scale energy storage power stations and is not suitable for vehicle-mounted power batteries because of the anti-seismic performance and the sealing problem of the electrolyte, and has particularly good fire safety performance when being used in large-scale energy storage power stations because of using the traditional liquid electrolyte and no combustible substances. The whole using process has no environmental protection pressure caused by processing waste batteries.

(2) The invention provides an economical battery energy storage and regeneration recycling technology based on the traditional liquid lead-acid battery, so that the service life of the battery is close to infinite circulation, the regeneration cost does not exceed 5% of the cost of newly purchasing a new battery after the service life of the battery is over, no waste is discharged, the environmental protection pressure after the battery is scrapped is avoided, the application cost of the storage battery in a large energy storage power station can be obviously reduced, and the economy and the environmental protection performance of the storage battery in the large energy storage power station are obviously improved.

Drawings

Fig. 1 is a schematic structural diagram of a detachable plate holder according to the present invention.

Fig. 2 is a cross-sectional view a-a of the removable plate holder of fig. 1.

Fig. 3 is a schematic diagram of the overall structure of the battery.

Fig. 4 is a B-B sectional view of the overall structure of the battery shown in fig. 3.

Fig. 5 is a schematic view of the shape of the positive and negative electrodes.

Fig. 6 is a schematic structural view of the repair groove.

Fig. 7 is a schematic diagram of a battery repair process.

Detailed Description

The present invention will be described in further detail with reference to the following drawings and specific examples, but the present invention is not limited thereto.

(1) on the structure of a common liquid lead-acid battery, lead electrodes of the storage battery are arranged on a detachable polar plate bracket, the structural schematic diagram of the detachable polar plate bracket is shown in figures 1 and 2, shallow grooves 2 adaptive to the thickness of the battery polar plates are formed on the side walls of two sides of the bracket of the detachable polar plate 1, and the positive polar plates and the negative polar plates are inserted into the shallow grooves 2 in a crossed manner so as to be fixed; therefore, the whole battery pole plate can be conveniently detached and moved, and the pole plate can be conveniently moved out for repairing after the performance of the battery pole plate is reduced or the service life of the battery pole plate is over;

(2) putting the whole support containing the positive and negative plates obtained in the step (1) into a battery shell 6, and then adding electrolyte (dilute sulfuric acid) to form the whole structure of the battery, as shown in fig. 3;

(a) first-stage repair: the battery pole plate to be repaired and the detachable pole plate support whole 104 are moved out of the battery tank and are placed in a prepared repairing tank, the structural schematic diagram of the repairing tank is shown in fig. 6, distilled water or deionized pure water 105 is injected into the repairing tank 101, an acid-resistant circulating pump 102 is arranged on the side of the repairing tank 101, and circulating water in the repairing tank 101 flows through gaps between the pole plates; the volume of the repair groove 101 is more than one time larger than that of the battery groove, and a detachable polar plate support 103 containing a new polar plate or a cleaned lead sulfate polar plate is additionally arranged in the repair groove 101; the method comprises the following steps of (1) enabling lead sulfate to be slightly soluble in water (the temperature is 0.041 g/kg water at 20 ℃), starting a circulating pump 102 and a power supply for 1 hour to enable the lead sulfate on the surface of a polar plate to be dissolved to be saturated, adding a pulse constant-current power supply to the positive electrode and the negative electrode of a battery of a new polar plate or a cleaned lead sulfate polar plate, controlling the pulse frequency to be 5-200 Hz and the duty ratio to be 70-90%, controlling the average current to be 5% of the battery capacity, (for example, controlling the charging current to be 50A by using a 1000 ampere-hour battery), controlling the open-circuit voltage of the pulse constant-current power supply to be 3-10 times of the battery voltage, and charging for 20 hours; during the charging process, lead ions dissolved in water obtain electrons on a new polar plate or a negative plate of the battery with a cleaned lead sulfate polar plate, the electrons become spongy pure lead, the electrons are lost on the positive plate, and the spongy pure lead is combined with oxygen ions in the water to generate lead dioxide; continuously reducing lead ions in water, reducing the concentration, continuously dissolving lead sulfate crystallized on a battery plate to be repaired, charging for 18-22 hours, basically dissolving the lead sulfate on the battery plate to be repaired to ensure that the capacity of the lead sulfate is recovered to more than 80% of the capacity of the primary battery, and if the white lead sulfate crystals on the surface are not obviously eliminated or cannot be recovered to more than 80% of the capacity by visual observation, continuously prolonging the charging time (namely cleaning time), prolonging the charging time by more than one time, and not recovering to 80% of the capacity of the primary battery, adopting a secondary repairing method. The aim of separating the pole plate to be repaired from the charging pole plate is to prevent pure cathode lead and anode lead dioxide which are charged and deposited from covering the lead sulfate crystals which need to be cleaned, and to ensure that the lead sulfate crystals are fully contacted and dissolved with water. Because a large energy storage station has a large number of battery packs, the work can be continuously and circularly carried out. Most of lead ions in the electrolyte in the repair tank are collected by electrolysis, but residual lead ions and sulfate ions from dissolved lead sulfate are remained in the solution. If the water is discharged randomly, the environment can be seriously polluted. But the water can be recycled without discharging. The cost of the treatment is very low, which is basically the cost of one-time charging, and is less than 0.5 percent of the cost of a newly-invested battery;

(2) secondary repair: the one-time repair service cycle of a general lead-acid battery plate does not exceed one thousand charge-discharge cycles, namely 2-3 years, after 3-5 first-level repairs, the method can not recover more than 80% of the capacity of a new battery, the battery plate can be moved out and placed in a pure water tank to be soaked for 25-40 minutes to wash away residual sulfuric acid (the soaking water can also be used for replenishing water to the battery), then the battery plate is moved out and drained, the plate is completely detached from a bracket and placed in a crucible to be melted, and as the specific gravity of lead is 11.3, the melting point is 327 ℃, the melting point of lead sulfate is 1087 ℃ and the specific gravity is 6.2, when the crucible is higher than 327 ℃, the lead plate is melted, the lead sulfate forms scum, the scum is removed and collected, the melted lead water is cast into the plate again, and lead water can contain trace lead sulfate particles, but the service performance of the plate is not influenced, and the lead sulfate scum is sent to a professional smeltery to be recovered, the lost lead sulfate supplements part of new lead and trace elements with the same formula as the original polar plate, so that the scrapping of the whole storage battery is avoided, the shell and the electrolyte are continuously reused, the cost for replacing the new battery is saved, a large amount of logistics and the commercial cost for recycling and selling the new battery are saved, and the environmental protection pressure caused by scrapping the whole battery is relieved. The cost for recasting the polar plate and supplementing a small amount of new lead is not more than 5 percent of that for resetting the new battery, the technical standard for resetting the new battery is achieved, a small amount of funds can be recovered by processing part of lead sulfate, and no waste is discharged in the whole process.

Claims

1. A storage battery energy storage and regeneration method for a large energy storage station is characterized by comprising the following steps:

(1) on the structure of a common liquid lead-acid battery, lead electrodes of the storage battery are arranged on a detachable polar plate bracket, and the side walls of two sides of the detachable polar plate bracket are provided with shallow grooves adaptive to the thickness of a battery polar plate, so that positive and negative polar plates are inserted into the shallow grooves in a crossed manner, and the positive and negative polar plates are fixed;

(2) putting the support containing the positive and negative plates obtained in the step (1) into a battery shell integrally, and then adding electrolyte to form an integral structure of the battery;

(3) repairing the battery plate, wherein the repairing is carried out in two stages:

(a) first-stage repair: the battery pole plate to be repaired and the detachable pole plate support are integrally moved out of the battery tank and placed in a prepared repairing tank, distilled water or deionized pure water is injected into the repairing tank, and a circulating pump is arranged at the edge of the repairing tank to enable circulating water in the repairing tank to flow through gaps between the pole plates; the volume of the repair groove is more than one time larger than that of the battery groove, and a detachable polar plate bracket containing a new polar plate or a cleaned lead sulfate polar plate is additionally arranged in the repair groove; starting a circulating pump and a power supply for 0.8-1.5 hours to dissolve lead sulfate on the surface of a polar plate to saturation, adding a pulse constant-current power supply to the positive and negative electrodes of a new polar plate or a battery with a cleaned lead sulfate polar plate, wherein the pulse frequency is 0.5-2000 Hz, the duty ratio is 20-90%, the average current is controlled to be 4-6% of the battery capacity, the open-circuit voltage of the pulse constant-current power supply is 3-10 times of the battery voltage, and the charging is carried out for 18-22 hours; during the charging process, lead ions dissolved in water obtain electrons on a new polar plate or a negative plate of the battery with a cleaned lead sulfate polar plate, the electrons become spongy pure lead, the electrons are lost on the positive plate, and the spongy pure lead is combined with oxygen ions in the water to generate lead dioxide; after 18-22 hours of charging, the concentration of lead ions in the electrolyte is reduced along with the charging process, the electrolyte reaches an unsaturated state, the solution continuously dissolves lead sulfate on a battery pole plate to be repaired, the pole plate with the dissolved lead sulfate is moved to a charging position for depositing lead and lead dioxide, and the capacity of the battery pole plate is recovered to be more than 80% of the capacity of a primary battery;

(b) secondary repair: after 3-5 times of primary repair, if the primary repair cannot recover more than 80% of the capacity of the new battery, secondary repair is adopted, the battery pole plate is moved out, the battery pole plate is placed into a pure water tank to be soaked for 25-40 minutes, residual sulfuric acid is washed away, the battery pole plate is moved out and drained, the pole plate is completely detached from the support and placed into a crucible to be melted, lead sulfate scum is removed and collected after the lead pole plate is melted when the crucible is higher than 327 ℃, melted lead water is cast into the pole plate again, the lead sulfate scum is sent to a professional smelter to be recycled, the lost lead sulfate replenishes part of new lead and trace elements of the original pole plate in the same formula and then is continuously used, thus the scrapping of the whole storage battery is avoided, and the shell and electrolyte are continuously reused.

2. The storage battery energy storage and regeneration method for the large energy storage station according to claim 1, wherein in the step (2), the electrolyte is dilute sulfuric acid.

3. The battery energy storage and regeneration method for large energy storage stations according to claim 1, wherein in step (3), the circulating pump is an acid-proof circulating pump.

4. The storage battery energy storage and regeneration method for the large energy storage station according to claim 1, wherein in the step (a), if the white lead sulfate crystals on the surface are not obviously eliminated or can not be recovered to more than 80% of the capacity by visual inspection, the cleaning and charging time is continuously prolonged, the charging time is prolonged by more than one time, and the capacity of the primary battery can not be recovered to more than 80%, and secondary repair is adopted.