CN105958077B - A kind of method of sol-gal process preparation four basic lead sulphate of little crystallite size - Google Patents
A kind of method of sol-gal process preparation four basic lead sulphate of little crystallite size Download PDFInfo
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- CN105958077B CN105958077B CN201610529851.4A CN201610529851A CN105958077B CN 105958077 B CN105958077 B CN 105958077B CN 201610529851 A CN201610529851 A CN 201610529851A CN 105958077 B CN105958077 B CN 105958077B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/20—Sulfates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of method of sol-gal process preparation four basic lead sulphate of little crystallite size takes lead acetate and complexing agent to be dissolved in distilled water under the conditions of stirring in water bath, and sulfuric acid solution and dispersing agent is then added, obtains lead oxide/sulfuric acid alucol；Lead oxide/sulfuric acid alucol continuation is stirred in a water bath, after being evaporated, in air atmosphere, passes through low temperature presintering knot and high temperature sintering respectively, obtains four basic lead sulphate powder, grind, sieving obtains four basic lead sulphates of little crystallite size.Advantage is: preparation process, condition and equipment are relatively easy, and four basic lead sulphate crystallite dimensions of synthesis are small, and Additive Properties are excellent as a positive electrode active material, and while increasing positive active material cycle life, its specific capacity can be improved.
Description
Technical field
The present invention relates to a kind of methods of sol-gal process preparation four basic lead sulphate of little crystallite size (4BS).
Background technique
Four basic lead sulphates (4BS) are one of the constituents of positive active material in solidification process, in formation process,
Coarseer α-the PbO of crystallite dimension can be converted into2。α-PbO2It can be used as active material skeleton, guarantee the smooth of charge and discharge
It carries out, improves the cycle life of lead-acid battery positive active material.In order to improve the ratio of 4BS in positive active material, usually
Way be that a part of 4BS is added during with lead plaster as crystal seed, to promote the formation of 4BS in solidification process.Quotient at present
The crystallite dimension of four basic lead sulphates (4BS) of industry is larger and is crossed-over, so that a part of 4BS in formation process
α-PbO can not be changed into2, will lead to specific capacity decline as additive.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of sol-gal processes to prepare four basic lead sulphate of little crystallite size
Method, the method preparation process, condition and equipment are relatively easy, and four basic lead sulphate crystallite dimensions of synthesis are small, as just
Pole active material additive is had excellent performance.
A kind of method of sol-gal process preparation four basic lead sulphate of little crystallite size, the specific steps of which are as follows:
1.1, it under the conditions of stirring in water bath, takes lead acetate and complexing agent to be dissolved in distilled water, sulfuric acid solution is then added
And dispersing agent, obtain lead oxide/sulfuric acid alucol；
1.2, continue lead oxide/sulfuric acid alucol that step 1.1 obtains to carry out water-bath at temperature identical as step 1.1
Stirring, is evaporated, obtains lead oxide/lead sulfate xerogel；
1.3, the lead oxide for obtaining step 1.2/lead sulfate xerogel passes through low temperature presintering knot in air atmosphere respectively
And high temperature sintering, obtain four basic lead sulphate powder；
1.4, the powder obtained step 1.3 is polished, crosses 200 meshes, obtains four alkali formula sulfuric acid of little crystallite size
Lead (4BS).
Further, the crystallite size of four basic lead sulphates of the little crystallite size is 500nm~1 μm.
Further, the molar ratio of the lead acetate and complexing agent is 1:1~1:3.
Further, the complexing agent is citric acid or EDTA.
Further, the temperature of heating water bath is 80 DEG C~90 DEG C.
Further, the mass concentration of the sulfuric acid solution is 15%~60%, and the sulfuric acid solution accounts for the total matter of lead acetate
The 3%~9% of amount.
Further, the dispersing agent is ethylene glycol, fumed silica or aluminum oxide.
Further, the mass ratio of the lead acetate and dispersing agent is 100:2~100:6.
Further, low temperature presintering junction temperature is 150 DEG C~250 DEG C, and sintering time is 1.5h~3.5h.
Further, high temperature sintering temperature is 300 DEG C~700 DEG C, and sintering time is 5h~7h.
Beneficial effects of the present invention:
(1) preparation process, condition and equipment are relatively easy, are point with ethylene glycol, fumed silica or aluminum oxide
Powder can prevent from reuniting between nanometer 4BS particle in synthesis process, can be improved the activity and change of four basic lead sulphates
At conversion ratio；The product purity of synthesis is higher, and four basic lead sulphate crystallite dimensions are small, is uniformly dispersed, can control in 500nm-1
μm, Additive Properties are excellent as a positive electrode active material.
(2) four basic lead sulphates of synthesis are added in positive active material 1%, are prepared into pole plate and are assembled into experimentally
Lead-acid battery.By constant current charge-discharge test it is found that being charged to 2.42V constant pressure with 0.25C electric current, respectively with 0.1C, 0.25C and
It discharges under 0.5C electric current, positive active material specific capacity can respectively reach 94.89mAh.g-1、86.42mAh.g-1With
70.78mAh.g-1.Under 0.5C charge and discharge, by 100 charge and discharge cycles, specific capacity does not obviously decay.Illustrate that benefit is added
With little crystallite size prepared by the present invention, four basic lead sulphate of high-purity (4BS), increasing positive active material cycle life
Meanwhile its specific capacity can be improved.
Detailed description of the invention
Fig. 1 is the XRD diagram of four basic lead sulphates of the invention；
Fig. 2 is the SEM figure of four basic lead sulphates of the invention；
Fig. 3 is four basic lead sulphates obtained using (corresponding embodiment 1) of the invention, is added to by the 1% of lead powder quality
In anode diachylon, the SEM figure of cured rear lead plaster；
Fig. 4 is four basic lead sulphates obtained using (corresponding embodiment 1) of the invention, is added to by the 1% of lead powder quality
In anode diachylon, the positive plate obtained after cured is assembled into 2V test-type lead-acid battery, is charged to 2.42V with 0.25C electric current
Constant pressure, respectively to discharge under 0.1C, 0.25C and 0.5C electric current, obtained charging and discharging curve；
Fig. 5 is four basic lead sulphates obtained using (corresponding embodiment 1) of the invention, is added to by the 1% of lead powder quality
In anode diachylon, cured obtained positive plate is assembled into 2V test-type lead-acid battery, is charged to 2.42V perseverance with 0.5C electric current
Pressure carries out cyclic charging and discharging test, obtained cycle performance curve to discharge into 1.75V under 0.5C electric current.
Specific embodiment
Embodiment
1.1, under the conditions of 80 DEG C~90 DEG C of stirring in water bath, the lead acetate and complexing agent dissolution that molar ratio is 1:1~1:3 are taken
In distilled water, the complexing agent is citric acid or EDTA, and sulfuric acid solution and dispersing agent, the matter of the sulfuric acid solution is then added
Measuring concentration is 15%~60%, and the sulfuric acid solution accounts for the 3%~9% of lead acetate gross mass, and the dispersing agent is ethylene glycol, gas
The mass ratio of aerosil or aluminum oxide, the lead acetate and dispersing agent is 100:2~100:6, obtains lead oxide/sulphur
Lead plumbate colloidal sol；
1.2, the lead oxide for obtaining step 1.1/sulfuric acid alucol continues under the conditions of 80 DEG C~90 DEG C of stirring in water bath, steams
It is dry, obtain lead oxide/lead sulfate xerogel；
1.3, the lead oxide for obtaining step 1.2/lead sulfate xerogel passes through 150 DEG C~250 in air atmosphere respectively
DEG C low temperature presintering knot 1.5h~3.5h and 300 DEG C~700 DEG C high temperature sintering 5h~7h, obtains four basic lead sulphate powder；
1.4, the powder obtained step 1.3 is polished, crosses 200 meshes, obtains four basic lead sulphates (4BS).This four
The crystallite size of basic lead sulphate is 500nm~1 μm.
Embodiment 1
1.1, lead acetate 6.5g and citric acid complexing agent 7.68g (molar ratio 1:2) are weighed, in 90 DEG C of stirring in water bath conditions
Under, it is dissolved in 100mL distilled water, the sulfuric acid solution that 0.58g mass concentration is 51%, the fumed silica of 0.28g is added
After dispersing agent, lead oxide/sulfuric acid alucol is obtained；
1.2, the lead oxide for obtaining step 1.1/sulfuric acid alucol continues under the conditions of 90 DEG C of stirring in water bath, after being evaporated
To lead oxide/lead sulfate xerogel；
1.3, the lead oxide for obtaining step 1.2/lead sulfate xerogel passes through 150 DEG C of low temperature in air atmosphere respectively
It is pre-sintered 3.5h and 500 DEG C of high temperature sintering 5h, obtains four basic lead sulphate powder；
1.4, the powder obtained step 1.3 is polished, crosses 200 meshes, obtains four basic lead sulphates (4BS).This four
The crystallite size of basic lead sulphate is 500nm~1 μm.
Four basic lead sulphates (4BS) that embodiment 1 obtains have been subjected to XRD test, have obtained the XRD diffraction maximum spectrum of material
Figure, as shown in Figure 1.It will be seen from figure 1 that the diffraction maximum and standard card of obtained four basic lead sulphate are very identical, material
The purity of material is relatively high.Although joined fumed silica point during synthesizing small-grain size lead sulfate (4BS)
Powder, but since fumed silica is non-crystal structure, there is no diffraction maximum appearance in XRD test, in calculated purity
The amount of fumed silica is not accounted in the process.
Four basic lead sulphates (4BS) that embodiment 1 obtains are scanned Electronic Speculum (SEM) test, obtained microscopic appearance
Figure, as shown in Figure 2.From figure 2 it can be seen that the crystal grain distribution of obtained four basic lead sulphate of little crystallite size (4BS) is equal
Even and grain size can control between 500nm~1 μm.This explanation can synthesize little crystal grain using method of the invention
Four basic lead sulphate of size (4BS).
Four basic lead sulphates (4BS) that embodiment 1 is obtained, are added in anode diachylon by the 1% of lead powder quality, pass through
Positive plate is obtained after solidification, and Electronic Speculum is scanned to it and is tested, obtained microscopic appearance figure, as shown in Figure 3.It can be with from Fig. 3
Find out there are a large amount of rodlike 4BS to occur in the positive active material after solidification, and be interweaved into network structure between particle,
Structural framework can be provided for positive active material.
Four basic lead sulphates (4BS) that embodiment 1 is obtained, are added in anode diachylon by the 1% of lead powder quality, pass through
The positive plate obtained after solidification is assembled into 2V test-type lead-acid battery with it, constant current charge-discharge test is carried out after being internalized into, is obtained
Charging and discharging curve under different discharge-rates, as shown in Figure 4.By constant current charge-discharge test it is found that with the charging of 0.25C electric current
To 2.42V constant pressure, respectively to discharge under 0.1C, 0.25C and 0.5C electric current, positive active material specific capacity can be respectively reached
94.89mAh.g-1、86.42mAh.g-1And 70.78mAh.g-1。
Four basic lead sulphates (4BS) that embodiment 1 is obtained, are added in anode diachylon by the 1% of lead powder quality, pass through
The positive plate obtained after solidification is assembled into 2V test-type lead-acid battery with it, cyclic charging and discharging test is carried out after being internalized into, is obtained
The cycle performance curve arrived, as shown in Figure 5.Test result shows under the conditions of 0.5C charge and discharge, follows by 100 charge and discharge
Ring, there is no obviously decaying for capacity.Illustrate that the four alkali formula sulphur synthesized using the present invention are added in plumbic acid positive active material
Lead plumbate (4BS) can also increase its specific capacity while improving positive active material cycle life.
Embodiment 2
1.1, lead acetate 6.5g and EDTA complexing agent 17.53g (molar ratio 1:3) is weighed, under the conditions of 80 DEG C of stirring in water bath,
It is dissolved in 100mL distilled water, the sulfuric acid solution that 0.20g mass concentration is 60%, the fumed silica dispersion of 0.13g is added
After agent, continue to stir, obtains lead oxide/sulfuric acid alucol；
1.2, the lead oxide for obtaining step 1.1/sulfuric acid alucol continues under the conditions of 80 DEG C of stirring in water bath, is evaporated, obtains
To lead oxide/lead sulfate xerogel；
1.3, the lead oxide for obtaining step 1.2/lead sulfate xerogel passes through 200 DEG C of low temperature in air atmosphere respectively
It is pre-sintered 2h and 400 DEG C of high temperature sintering 6h, obtains four basic lead sulphate powder；
1.4, the powder obtained step 1.3 is polished, crosses 200 meshes, obtains four basic lead sulphates (4BS).
Embodiment 3
1.1, lead acetate 6.5g and citric acid complexing agent 3.84g (molar ratio 1:1) are weighed, in 85 DEG C of stirring in water bath conditions
Under, it is dissolved in 100mL distilled water, the sulfuric acid solution that 0.58g mass concentration is 15%, the aluminum oxide point of 0.39g is added
After powder, lead oxide/sulfuric acid alucol is obtained；
1.2, the lead oxide for obtaining step 1.1/sulfuric acid alucol continues under the conditions of 85 DEG C of stirring in water bath, after being evaporated
To lead oxide/lead sulfate xerogel；
1.3, the lead oxide for obtaining step 1.2/lead sulfate xerogel passes through 550 DEG C of low temperature in air atmosphere respectively
It is pre-sintered 1.5h and 300 DEG C of high temperature sintering 7h, obtains four basic lead sulphate powder；
1.4, the powder obtained step 1.3 is polished, crosses 200 meshes, obtains four basic lead sulphates (4BS).
Embodiment 4
1.1, lead acetate 6.5g and citric acid complexing agent 7.68g are weighed, under the conditions of 90 DEG C of stirring in water bath, is dissolved in
In 100mL distilled water, 0.58g mass concentration is added as 30% sulfuric acid solution, after the ethylene glycol dispersing agent of 0.30g, obtains oxygen
Change lead/sulfuric acid alucol；
1.2, the lead oxide for obtaining step 1.1/sulfuric acid alucol continues under the conditions of 90 DEG C of stirring in water bath, after being evaporated
To lead oxide/lead sulfate xerogel；
1.3, the lead oxide for obtaining step 1.2/lead sulfate xerogel passes through 550 DEG C of low temperature in air atmosphere respectively
It is pre-sintered 1.5h and 700 DEG C of high temperature sintering 5h, obtains four basic lead sulphate powder；
1.4, the powder obtained step 1.3 is polished, crosses 200 meshes, obtains four basic lead sulphates (4BS).
Four basic lead sulphates (4BS) of 1 embodiment of the present invention 2~4 of table are added to positive lead by the 1% of lead powder quality
The electrode assembling prepared in cream at 2V test-type lead-acid battery chemical property table
The above is only specific embodiments of the present invention, are not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of method of sol-gal process preparation four basic lead sulphate of small size, it is characterized in that:
Specific step is as follows:
1.1, under the conditions of stirring in water bath, lead acetate and complexing agent is taken to be dissolved in distilled water, sulfuric acid solution is then added and divided
Powder obtains lead oxide/sulfuric acid alucol；
The molar ratio of the lead acetate and complexing agent is 1:1~1:3；
The complexing agent is citric acid or EDTA；
The dispersing agent is ethylene glycol, fumed silica or aluminum oxide；
The mass ratio of the lead acetate and dispersing agent is 100:2~100:6；
1.2, lead oxide/sulfuric acid alucol that step 1.1 obtains is continued the progress water-bath at temperature identical as step 1.1 to stir
It mixes, is evaporated, obtain lead oxide/lead sulfate xerogel；
1.3, the lead oxide for obtaining step 1.2/lead sulfate xerogel passes through low temperature presintering knot and height in air atmosphere respectively
Temperature sintering, obtains four basic lead sulphate powder；
1.4, the powder obtained step 1.3 is polished, crosses 200 meshes, obtains the little crystal grain that crystallite size is 500nm-1 μm
Four basic lead sulphates (4BS) of size.
2. the method for sol-gal process preparation four basic lead sulphate of small size according to claim 1, it is characterized in that: water-bath
The temperature of heating is 80 DEG C~90 DEG C.
3. the method for sol-gal process preparation four basic lead sulphate of small size according to claim 1, it is characterized in that: described
The mass concentration of sulfuric acid solution is 15%~60%, and the sulfuric acid solution accounts for the 3%~9% of lead acetate gross mass.
4. the method for sol-gal process preparation four basic lead sulphate of small size according to claim 1, it is characterized in that: low temperature
Pre-sintering temperature is 150 DEG C~250 DEG C, and sintering time is the h of 1.5h~3.5.
5. the method for sol-gal process preparation four basic lead sulphate of small size according to claim 1, it is characterized in that: high temperature
Sintering temperature is 300 DEG C~700 DEG C, and sintering time is 5h~7h.
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| CN107265497B (en) * | 2017-05-22 | 2019-11-15 | 安徽徽能化工科技有限公司 | A method of extending yellow lead energy-saving production technology and prepares four basic lead sulphates |
| CN109133160B (en) * | 2018-08-28 | 2020-09-25 | 浙江工业大学 | Preparation method of small crystal size 4BS additive for high-performance battery |
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