CN113224312B - Titanium/copper-based long-life high-power lead-acid storage battery and preparation method thereof - Google Patents
Titanium/copper-based long-life high-power lead-acid storage battery and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lead-acid storage batteries, and particularly relates to a titanium/copper-based long-life high-power lead-acid storage battery and a preparation method thereof. The titanium/copper-based long-life high-power lead-acid storage battery has the electrochemical characteristics of a common lead-acid battery, has the characteristics of long service life and high power, particularly compared with the traditional lead-acid battery manufacturing process, the invention cancels the procedures of lead powder preparation, lead paste preparation, plate coating, curing and formation, reduces the equipment investment, greatly reduces the contact link with heavy metal lead, and changes the traditional manufacturing process and flow of the lead-acid battery.
Description
Technical Field
The invention belongs to the technical field of lead-acid storage batteries, and particularly relates to a titanium/copper-based long-life high-power lead-acid storage battery and a preparation method thereof.
Background
As a traditional secondary chemical power source, a lead-acid battery is continuously occupied by new chemical power sources such as lithium ion batteries and fuel cells in various application fields such as energy storage, power, start and stop. Particularly, with the further compression of the manufacturing cost per ampere hour of the lithium ion battery and the recognition problem of people, the lead-acid battery seems to gradually lose the inherent price advantage, and further, the ever-increasing cost performance of the lithium ion battery is highlighted. But lead-acid batteries have the largest market share and the widest application range in the chemical power supply market, and are difficult to replace by other novel power supplies for a long time. But has significant disadvantages such as low mass specific energy, large volume, poor power performance and short cycle life. More serious, the lead is used in a large amount, and the environment and resources are not influenced very much. In the manufacturing process of the lead-acid storage battery, special lead powder preparation, lead plaster preparation, grid manufacturing, lead plaster coating, curing, formation and other processes are needed, lead-related rings are more in sections, investment cost is high, and environmental protection pressure is high. In addition, the traditional grid structure and the tubular structure (tubular positive electrode) of the lead-acid storage battery grid both need thicker electrodes, so that enough active material quantity is ensured; the larger the thickness of the electrode is, the more lead is used, the gravimetric specific energy of the battery is reduced, and the current potential distribution of different parts of the electrode and the utilization rate of active substances at different depths of the electrode have larger difference, so that the overall power characteristic of the battery is influenced.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method adopts the method that lead dioxide is deposited on a titanium foil or an aluminum foil to be used as a positive electrode, and lead is plated on a copper foil or a lead foil to be used as a negative electrode, so that the effects of small lead consumption, long service life and remarkably improved power performance of the lead-acid battery are realized.
The invention relates to a titanium/copper-based long-life high-power lead-acid storage battery, wherein a titanium-based or aluminum-based lead dioxide porous electrode is adopted as a positive electrode, a copper-based or lead-based lead-plated electrode is adopted as a negative electrode, an electrolyte is a sulfuric acid solution containing sodium lignosulfonate and dysprosium fluoride, and a thin glass fiber AGM material is adopted as a partition plate.
The assembly process of the titanium/copper-based long-life high-power lead-acid storage battery is as follows: and (2) placing n positive electrodes and n +1 negative electrodes in a crossed manner, wherein n is an integer of 30-300, placing a partition plate between one positive electrode and one negative electrode, arranging plate lugs on the positive electrode and the negative electrode, connecting the positive plate lug and the negative plate lug through connecting screws, placing the positive plate lug and the negative plate lug into a battery jar, and finally injecting prepared electrolyte to finish assembly. The number of the positive electrode and the negative electrode can be flexibly changed according to the capacity and the design requirement.
The preparation method of the titanium-based or aluminum-based lead dioxide porous electrode of the titanium/copper-based long-life high-power lead-acid storage battery comprises the following steps:
titanium foil or aluminum foil → thermokalite ultrasonic degreasing → deionized water cleaning → soaking mixed acid to remove oxide layer → deionized water cleaning → hydrochloric acid etching → deionized water cleaning → tin dioxide/antimony substrate coating → thermal oxidation → electroplating method to deposit lead dioxide layer → deionized water cleaning → drying (80 ℃ C.) → titanium base or aluminum base lead dioxide porous electrode.
The thickness of the titanium foil or the aluminum foil is 0.2mm, the length and the width of the titanium foil or the aluminum foil are cut according to actual requirements and are rectangular, and a lug with the width of 10mm, the height of 15mm and the diameter of 6mm is reserved above the titanium foil or the aluminum foil. In addition, in the process of preparing the titanium-based lead dioxide electrode, in order to prevent warping and deformation, the bottom edge and two side frames of the titanium foil or the aluminum foil are fixed and shaped by using plastic frames and are removed when the battery is assembled.
The preparation method of the copper-based or lead-based lead-plated electrode of the titanium/copper-based long-life high-power lead-acid storage battery comprises the following steps:
copper foil or lead foil → hot alkali ultrasonic degreasing → deionized water cleaning → soaking mixed acid to remove oxide layer → deionized water cleaning → electroplated lead → deionized water cleaning → hot water cleaning (not less than 60 ℃) → drying (not less than 80 ℃) → copper base or lead base lead-plated electrode.
The thickness of the copper foil or the lead foil is 0.1mm, the length and the width of the copper foil or the lead foil are cut according to actual requirements and are rectangular, and a lug with the width of 10mm, the height of 15mm and the diameter of 6mm is reserved above the copper foil or the lead foil. In addition, in the process of preparing the copper foil or lead foil lead-plated negative electrode, in order to prevent warping and deformation, the bottom edge and two side frames of the copper foil or lead foil are fixed and shaped by using plastic frames and are removed when the battery is assembled.
When electroplating lead, firstly 3mA/cm is used 2 Current density of (3), 10 min; then 6mA/cm was used 2 20mi n.
The preparation method of the electrolyte of the titanium/copper-based long-life high-power lead-acid storage battery comprises the following steps: completely dissolving sodium lignosulfonate and dysprosium fluoride in deionized water, slowly adding concentrated sulfuric acid with the mass percent of 96%, uniformly stirring, cooling at room temperature for later use, wherein the mass ratio of the sodium lignosulfonate to the dysprosium fluoride to the concentrated sulfuric acid is 8-12:1-3:6000-7000:3000-4000, preferably 10:2:6600: 3400.
The separator is made of superfine glass fiber, the thickness of the separator is 0.5mm under the condition of 10kPa, 1% of organic fiber filaments with the reinforcing effect are embedded in the separator, and the compression rate of the separator is controlled between 10% and 15% in the assembling process of the separator and the positive electrode and the negative electrode.
The positive electrode of the invention adopts titanium foil as a substrate, the density is one third of that of lead, the corrosion resistance is excellent, the shape and the size are stable, the mechanical strength is good, and the problems of bending deformation and the like can not occur, thereby ensuring high mass specific energy and long service life of the battery.
The negative electrode of the invention adopts the copper foil as a matrix, the density is 70 percent of that of lead, and the conductivity is more than ten times of that of lead, thereby further ensuring the high mass specific energy and power performance of the battery.
The thickness of the anode titanium matrix is 0.2mm, the thickness of the cathode copper matrix is 0.1mm, the contact between an active substance and electrolyte is greatly improved while the service life of the battery is ensured and the consumption of metal materials is reduced, and the power characteristic of the battery is improved.
The sodium lignosulfonate serving as the traditional negative electrode expanding agent of the lead-acid battery is dissolved in the electrolyte, so that the influence of no low-temperature auxiliary agent added in the negative electrode lead plating is made up, and the low-temperature performance of the battery is ensured; the added rare earth fluoride is a hydrogen precipitation inhibitor optimized through a large number of tests, so that hydrogen precipitation in the charging process can be effectively reduced, and water loss of the battery is reduced.
The thin (0.5mm) AGM separator with the embedded organic fiber yarns not only ensures the amount of sulfuric acid electrolyte required by the reaction, but also can effectively prevent the short circuit of dendrites in the use process of the battery.
The plate lug is provided with a hole in the middle, and the connecting screw is used for replacing the traditional bus bar, so that the use of lead is further reduced, and the problem of welding titanium/copper and terminal post materials is solved.
The invention carries out hydrochloric acid etching on the titanium foil to realize the honeycomb structure of the electrode, thereby greatly improving the real reaction area of the electrode and improving the discharge capacity of the battery.
When the negative electrode is used for plating lead, a smaller current density is used in the early stage to generate a more compact plating layer, the binding force between the plating layer and the matrix is improved, and a larger current density is used in the middle and later stages, so that the plating layer is porous while the strength of the plating layer is ensured, the reaction area of the electrode is further improved, and the capacity of the battery is increased.
Compared with the prior art, the invention has the following beneficial effects:
the titanium/copper-based long-life high-power lead-acid storage battery provided by the invention has the electrochemical characteristics of a common lead-acid battery, has the characteristics of long service life and high power, and particularly, compared with the traditional lead-acid battery manufacturing process, the invention cancels the procedures of lead powder preparation, lead paste preparation, plate coating, curing and formation, reduces the equipment investment, greatly reduces the contact link with heavy metal lead, and changes the traditional manufacturing process and flow of the lead-acid battery.
Drawings
FIG. 1 is a front and side view of a positive electrode according to the present invention;
FIG. 2 is a schematic view of a negative electrode structure according to the present invention;
fig. 3 is a front view and a side view of the battery pole group according to the present invention.
In the figure: 1. a titanium foil; 2. a tin dioxide/antimony coating; 3. a lead dioxide deposition layer; 4. an electrode connection hole; 5. copper foil; 6. plating a lead layer; 7. a positive plate; 8. an AGM separator; 9. a negative plate; 10. positive/negative plate lugs.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples.
Example 1
According to the structure of FIG. 1, a titanium foil with the thickness of 0.2mm is cut, the width W is 60mm, the height H is 60mm, the width a of the lug is 10mm, the height is 20mm, and the radius of the electrode connecting hole is 3 mm. After the cut titanium foil is shaped at the frame by using a PP plastic frame, the following operations are carried out in sequence:
(1) ultrasonic degreasing in 80 deg.C sodium hydroxide hot alkali for 8h, and completely cleaning with deionized water for 5 min;
(2) soaking mixed acid (110 g of sulfuric acid, 30g of nitric acid, 2g of hydrochloric acid and 400g of deionized water) to remove an oxide layer, and completely cleaning the oxide layer with the deionized water;
(3) etching with hydrochloric acid (mass percent: 18%) for 2h, and completely cleaning with deionized water;
(4) dissolving tin tetrachloride and antimony trichloride in a hydrochloric acid solution with the molar ratio of 6:1 of 20%, uniformly mixing, adding a n-butanol solvent with the concentration of 5%, uniformly coating the two sides of a titanium foil after completely mixing, drying the titanium foil in an air-blast drying oven at 100 ℃ for 5min, then placing the titanium foil in a muffle furnace at 510 ℃, heating the titanium foil for 10min, repeatedly coating a mixture of tin tetrachloride and antimony trichloride, drying the titanium foil at 100 ℃ and heating the titanium foil at 510 ℃ for more than 10 times, and repeatedly preparing a tin-antimony coating;
(5) In an electrolyte (containing 1% of potassium dichromate) containing a sodium hydroxide solution (150g/L) of lead oxide (20.10g/L), a lead dioxide layer is deposited by an electroplating method, the current is set to be 220mA, the time is 1h, and the water bath temperature is 40 ℃;
(6) adding 1% of silver nitrate into a nitric acid (10g/L) electrolyte containing lead nitrate (250g/L) and a sodium fluoride solution (0.5g/L), and depositing a lead dioxide layer by an electroplating method, wherein the current is set to 2200mA, the time is 1h, and the water bath temperature is 60 ℃; and washing with deionized water, and drying (at the temperature of more than or equal to 80 ℃) to obtain the titanium-based lead dioxide porous anode for later use.
According to the structure of fig. 2, a copper foil with a thickness of 0.1mm is cut, the width W is 60mm, the height H is 60mm, the width a of the lug is 10mm, the height is 20mm, and the radius of the electrode connection hole is 3 mm. And sequentially carrying out the following operations on the cut copper foil:
(1) ultrasonic degreasing in 80 deg.C sodium hydroxide hot alkali for 8h, and completely cleaning with deionized water for 5 min;
(2) washing with 60 ℃ deionized water, and completely washing with tap water;
(3) soaking mixed acid (110 g of sulfuric acid, 30g of nitric acid, 2g of hydrochloric acid and 400g of deionized water) to remove an oxide layer, and completely cleaning the oxide layer with the deionized water;
(4) electroplating lead: applying current to a solution (plating solution density of 1.28g/ml) containing 200g of hydrofluoric acid, 180g of boric acid, 240g of lead oxide and 2g of bone glue, at current values of 288mA for 10 min; 576mA, and a water bath temperature of 30 ℃ for 20 min.
(5) And completely cleaning with tap water, cleaning with deionized water at 60 ℃ for 1min, and drying with a forced air drying oven at 80 ℃ for 15min to obtain the lead-plated cathode for later use.
Removing a plastic frame, alternately arranging 100 prepared titanium-based lead dioxide electrodes and 101 copper foil lead-plated cathodes according to the mode of a figure 3, placing an AGM separator between each positive electrode and each negative electrode, wherein the AGM separator is made of superfine glass fiber, the thickness of the AGM separator is 0.5mm under the condition of 10kPa, 1% of organic fiber filaments with the reinforcing effect are embedded in the AGM separator, and the compressibility of the AGM separator is controlled to be 10% -15% in the assembling process of the AGM separator, the positive electrode and the negative electrode.
The positive plate lug and the negative plate lug are respectively connected through the electrode connecting hole by using a screw, so that the respective electronic connection of the positive plate lug and the negative plate lug is realized, and the positive plate lug and the negative plate lug are placed into the battery jar.
Completely dissolving 10g of sodium lignosulphonate and 2g of dysprosium fluoride in 6600g of deionized water, slowly adding 3400g of concentrated sulfuric acid with the mass percent of 96%, uniformly stirring, and cooling at room temperature for later use.
And (3) pouring 220g of prepared electrolyte into a battery jar, standing for 10min to obtain the titanium/copper-based lead-acid battery with the voltage of 2V/3.2Ah and the weight of 920g, and carrying out subsequent performance test.
1C discharging: 3.2 discharging, and stopping the voltage by 1.5V;
And (3) testing the cycle life:
discharging: 1.6A discharge, the end voltage is 1.75V;
charging: 0.8A/2.4V, constant current voltage limiting 6h, 0.1A, 2 h;
the above is one cycle.
The parameters of the sample cell are compared to those of a conventional lead acid cell in the following table.
| Battery with a battery cell | Mass specific energy wh/kg | 1C discharge | Cycle life (2hr) | Failure mode |
| Sample cell | 44.1 | 50min | 448 | Short circuit of spacer dendrite |
| Reference cell | 34.5 | 40min | 366 | Corrosion of positive grid |
Example 2
According to the structure of FIG. 1, a titanium foil with the thickness of 0.2mm is cut, the width W is 60mm, the height H is 60mm, the width a of the lug is 10mm, the height is 20mm, and the radius of the electrode connecting hole is 3 mm. The cut titanium foil is shaped at the frame by a PP plastic frame, and then the following operations are sequentially carried out:
(1) ultrasonic degreasing in 80 deg.C sodium hydroxide hot alkali for 8h, and completely cleaning with deionized water for 5 min;
(2) soaking mixed acid (110 g of sulfuric acid, 30g of nitric acid, 2g of hydrochloric acid and 400g of deionized water) to remove an oxide layer, and completely cleaning the oxide layer with the deionized water;
(3) etching with hydrochloric acid (mass percent: 18%) for 2h, and completely cleaning with deionized water;
(4) dissolving stannic chloride and antimony trichloride in a hydrochloric acid solution with a molar ratio of 6:1 in a 20% solution, uniformly mixing, adding a n-butanol solvent with a concentration of 5%, uniformly coating the mixture on two sides of a titanium foil 1 after complete mixing, placing the titanium foil in an air-blowing drying oven to dry for 5min at 100 ℃, then placing the titanium foil in a muffle furnace to heat for 10min at 510 ℃, repeatedly coating a mixture of stannic chloride and antimony trichloride, drying at 100 ℃ and heating at 510 ℃ for more than 10 times, and repeatedly preparing to obtain a stannum-antimony coating;
(5) In an electrolyte (containing 1% of potassium dichromate) containing a sodium hydroxide solution (150g/L) of lead oxide (20.10g/L), a lead dioxide layer is deposited by an electroplating method, the current is set to be 220mA, the time is 1h, and the water bath temperature is 40 ℃;
(6) adding 1% silver nitrate into a nitric acid (10g/L) electrolyte containing 250g/L lead nitrate and 0.5g/L sodium fluoride solution, and depositing a lead dioxide layer 3 by an electroplating method, wherein the current is set to 2200mA, the time is 1h, and the water bath temperature is 60 ℃; and washing with deionized water, and drying (at the temperature of more than or equal to 80 ℃) to obtain the titanium-based lead dioxide porous anode for later use.
According to the structure of fig. 2, a copper foil with a thickness of 0.1mm is cut, the width W is 60mm, the height H is 60mm, the width a of the lug is 10mm, the height is 20mm, and the radius of the electrode connection hole is 3 mm. And sequentially carrying out the following operations on the cut copper foil:
(1) ultrasonic degreasing in 80 deg.C sodium hydroxide hot alkali for 8h, and completely cleaning with deionized water for 5 min;
(2) washing with 60 ℃ deionized water, and completely washing with tap water;
(3) soaking mixed acid (110 g of sulfuric acid, 30g of nitric acid, 2g of hydrochloric acid and 400g of deionized water) to remove an oxide layer, and completely cleaning the oxide layer with the deionized water;
(4) electroplating lead: applying an electric current to a solution (plating solution density of 1.28g/ml) containing HF200g, boric acid 180g, lead oxide 240g, and bone glue 2g, at respective current values of 288mA for 10 min; 576mA, 20min, and a water bath temperature of 30 ℃.
(5) And completely cleaning with tap water, cleaning with deionized water at 60 ℃ for 1min, and drying with a forced air drying oven at 80 ℃ for 15min to obtain the lead-plated cathode for later use.
Removing a plastic frame, alternately arranging 200 prepared titanium-based lead dioxide electrodes and 201 copper foil lead-plated cathodes according to the mode of a figure 3, placing an AGM separator between each positive electrode and each negative electrode, wherein the AGM separator is made of superfine glass fiber, the thickness of the AGM separator is 0.5mm under the condition of 10kPa, 1% of organic fiber filaments with the reinforcing effect are embedded in the AGM separator, and the compressibility of the AGM separator is controlled to be 10% -15% in the assembling process of the AGM separator, the AGM separator and the positive electrode and the negative electrode.
The positive plate lug and the negative plate lug are connected through the electrode connecting hole by using two screws, so that the respective electronic connection of the positive plate lug and the negative plate lug is realized, and the positive plate lug and the negative plate lug are placed in the battery jar.
Completely dissolving 10g of sodium lignosulphonate and 2g of dysprosium fluoride in 6600g of deionized water, slowly adding 3400g of concentrated sulfuric acid with the mass percent of 96%, uniformly stirring, and cooling at room temperature for later use.
440g of the prepared electrolyte is poured into a battery jar with the size of 14.5cm multiplied by 12.5cm multiplied by 8cm, and the titanium/copper-based lead-acid battery with the voltage of 2V/6.4Ah and the weight of 1840g is obtained after standing for 10min for subsequent performance test.
1C discharging: 6.4A discharge, the end voltage is 1.5V;
And (3) testing the cycle life:
discharging: 3.2A discharge, and the final voltage is 1.75V;
charging: 1.6A/2.4V, constant current voltage limiting 6h, 0.1A, 2 h;
the above is one cycle.
The parameters of the sample cell are compared to those of a conventional lead acid cell in the following table.
| Battery with a battery cell | Mass specific energy wh/kg | 1C discharge | Cycle life (2hr) | Failure mode |
| Sample cell | 45.2 | 55min | 450 | Short circuit of spacer dendrite |
| Reference cell | 34.5 | 40min | 366 | Corrosion of positive grid |
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (6)
1. A titanium/copper-based long-life high-power lead-acid storage battery is characterized in that: the anode adopts a titanium-based or aluminum-based lead dioxide porous electrode, the cathode adopts a copper-based or lead-based lead-plated electrode, the electrolyte is a sulfuric acid solution containing sodium lignosulfonate and dysprosium fluoride, and the separator adopts a thin glass fiber AGM material;
the assembly process is as follows: placing n positive electrodes and n +1 negative electrodes in a crossed manner, wherein n is an integer of 30-300, placing a partition plate between one positive electrode and one negative electrode, arranging plate lugs on the positive electrode and the negative electrode, connecting the positive plate lug and the negative plate lug through connecting screws, placing the positive plate lug and the negative plate lug into a battery jar, and finally injecting prepared electrolyte to finish assembly;
The preparation method of the titanium-based or aluminum-based lead dioxide porous electrode comprises the following steps:
titanium foil or aluminum foil → thermokalite ultrasonic degreasing → deionized water cleaning → soaking mixed acid to remove the oxide layer → deionized water cleaning → hydrochloric acid etching → deionized water cleaning → tin dioxide/antimony substrate coating → thermal oxidation → electroplating method to deposit the lead dioxide layer → deionized water cleaning → drying → titanium base or aluminum base lead dioxide porous electrode;
the preparation method of the copper-based or lead-based lead-plated electrode comprises the following steps:
copper foil or lead foil → thermokalite ultrasonic degreasing → deionized water cleaning → soaking mixed acid to remove an oxidation layer → deionized water cleaning → electrolytic lead plating → deionized water cleaning → hot water cleaning → drying → copper base or lead base lead plating electrode.
2. The titanium/copper-based long-life high-power lead-acid battery as claimed in claim 1, wherein: the thickness of the titanium foil or the aluminum foil is 0.2mm, the titanium foil or the aluminum foil is rectangular, and a lug with a circular hole inside is arranged above the titanium foil or the aluminum foil.
3. The titanium/copper-based long-life high-power lead-acid battery as claimed in claim 1, wherein: the thickness of the copper foil or the lead foil is 0.1mm, the copper foil or the lead foil is rectangular, and a lug with a round hole inside is arranged above the copper foil or the lead foil.
4. The titanium/copper-based long-life high-power lead-acid battery as claimed in claim 1, wherein: when electroplating lead, firstly 3mA/cm is used 2 Current density of (3), 10 min; then 6mA/cm was used 2 20 min.
5. The titanium/copper-based long-life high-power lead-acid battery as claimed in claim 1, wherein: the preparation method of the electrolyte comprises the following steps: completely dissolving sodium lignosulfonate and dysprosium fluoride in deionized water, slowly adding concentrated sulfuric acid with the mass percent of 96%, uniformly stirring, and cooling at room temperature for later use, wherein the mass ratio of the sodium lignosulfonate to the dysprosium fluoride to the concentrated sulfuric acid is 8-12:1-3:6000-7000: 3000-4000.
6. The titanium/copper-based long-life high-power lead-acid battery as claimed in claim 1, wherein: the separator is made of superfine glass fiber, has a thickness of 0.5mm under 10kPa, is embedded with 1% of organic fiber filaments with a reinforcing effect by mass fraction, and has a compression ratio of 10-15% in the process of assembling with the positive electrode and the negative electrode.
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