CN110010899A - A kind of nanometer of basic lead carbonate-carbon composite and its preparation method and application - Google Patents
A kind of nanometer of basic lead carbonate-carbon composite and its preparation method and application Download PDFInfo
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- CN110010899A CN110010899A CN201910381725.2A CN201910381725A CN110010899A CN 110010899 A CN110010899 A CN 110010899A CN 201910381725 A CN201910381725 A CN 201910381725A CN 110010899 A CN110010899 A CN 110010899A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The present invention provides a kind of nanometer of basic lead carbonate-carbon composites, it is characterised in that: is made of carbon material and the nanometer basic lead carbonate particles for being dispersed in the carbon material surface, the nanometer basic lead carbonate particles are in 150nm or less.Nanometer basic lead carbonate-carbon composite of the present invention can preferably delay the irreversible sulfation of cathode, preferably inhibition evolving hydrogen reaction as lead carbon battery cathode additive agent.Easy to operate the present invention also provides nanometer basic lead carbonate-carbon composite preparation method, low in cost, not harsh to production equipment and working condition, obtained basic lead carbonate size is small and is evenly dispersed on the surface of carbon material.The present invention also provides the nanometer basic lead carbonate-application of the carbon composite as lead carbon battery negative electrode active material in lead carbon battery.
Description
Technical field
The present invention relates to lead carbon battery technical field, more particularly, to a kind of nanometer of basic lead carbonate-carbon composite and
Preparation method and application.
Background technique
Cheap, safe and reliable, use temperature range is wide, recovery efficiency is high, stored energy capacitance because having for lead-acid battery
The advantages such as big, be widely used in various electrical vehicular powers, engine starting, communication base station, new energy energy storage and not between
The fields such as power-off source；However, lead-acid battery under high magnification partial state of charge, is failed due to the easy sulfation of negative plate.
Lead carbon battery be using high-specific surface area, Fabrication of High Specific Capacitance, highly conductive carbon material as a kind of novel lead-acid battery of cathode additive agent,
The advantages of having lead-acid accumulator and supercapacitor concurrently, with excellent cycle life and greatly under high magnification partial state of charge
Current charge-discharge electrical property.
Lead carbon battery is in cyclic process, and especially phase, the overpotential of hydrogen evolution of negative plate carbon material compare metal after charging
Lead is much lower, is easy catalytic electrolysis elutriation and goes out hydrogen, therefore in the end-of-cycle charging process of battery, what is quickly generated is a large amount of
Hydrogen cannot be reacted with the oxygen that anode generates in time generates water, so that bulk gas is precipitated from inside battery, leads to electricity
It solves water content in liquid to reduce, sour specific gravity increases, and exacerbates the corrosion to grid.Bubble impact pole plate during gas evolution,
Certain physical trauma is caused to pole plate, so that the active material of pole plate falls off, leads to battery capacity and service life reduction.Therefore,
It is necessary to which the metallic lead of high overpotential of hydrogen evolution or its esters substance are loaded to carbon material to inhibit evolving hydrogen reaction, common leaded is closed
Object has lead oxide, lead sulfate etc., and lead oxide, lead sulfate will all become spongy lead in post-conversion, and substantially play the role of all
It is to be eventually converted into spongy lead, improves the overpotential of hydrogen evolution of carbon material itself.
Summary of the invention
In view of the above technical problems, the purpose of the present invention is to provide a kind of nanometer of basic lead carbonate-carbon composites, originally
Invention additionally provides a kind of nanometer of basic lead carbonate-carbon composite preparation method, and the present invention still further provides described receive
Application of the rice basic lead carbonate-carbon composite as lead carbon battery negative electrode active material in lead carbon battery.
The technical solution adopted by the present invention is that:
A kind of nanometer of basic lead carbonate-carbon composite by carbon material and is dispersed in receiving for the carbon material surface
Rice basic lead carbonate particles composition, the nanometer basic lead carbonate particles are in 150nm or less.The nanometer basic lead carbonate particles
Size it is small, the lead sulfate that can be avoided big crystal is formed, and the irreversible sulfuric acid leaded of negative plate, the irreversible sulfuric acid of negative plate are delayed
Salinization is substantially exactly that the lead sulfate of bulky grain cannot be converted into spongy lead.
Nanometer basic lead carbonate-carbon composite of the present invention, wherein the carbon material is coconut carbon, rice hull carbon
It is low with one of graphene or two or more mixtures, the carbon material large specific surface area, hydrogen-evolution overpotential；The carbon materials
The overpotential of hydrogen evolution of material is at least in 0.8V or more, and specific surface area is at least in 1000m2/G or more, specific capacitance at least 120F/g with
On, it is platinum electrode to electrode that reference electrode, which is mercury/Mercurous sulfate electrode, and electrolyte is the sulfuric acid solution of 1.28g/ml.The carbon
Material is the carbon material with high overpotential of hydrogen evolution, high-specific surface area and high specific capacitance, and the carbon material of high hydrogen-evolution overpotential can subtract
The load capacity of nanometer basic lead carbonate, the carbon of high specific capacitance can be improved in the fluid loss of few battery, the carbon material of high-specific surface area
Material can make battery play the role of supercapacitor fast energy storage in large current charge, to improve charging by energy
Power.
The preparation method of nanometer basic lead carbonate-carbon composite of the present invention, comprising the following steps:
(1) prepared by solution A: lead source being added in beaker, deionized water is then added, stirs completely molten to the lead source
Solution, obtains solution A, and the mass concentration of the solution A is 2.5-10%；
(2) prepared by solution B: carbon material being added in solution A described in step (1), then magnetic agitation 0.5-1h, makes
It obtains lead ion and the carbon material is evenly dispersed in deionized water, obtain solution B, the throwing in the lead source and the carbon material
Expect than being calculated as 0.3-5 with the mass ratio of lead element and the carbon material；
(3) precursor preparation: strong base solution is added drop-wise in solution B described in step (2), magnetic agitation 0.5-1h, very
Solid is put into drying in vacuum oven by empty pump filter, obtains presoma, and the mass concentration of the strong base solution is 2.5-
10%；
(4) prepared by product: presoma described in step (3) being pulverized, is roasted in protective atmosphere, is then dropped naturally
Temperature obtains product nano basic lead carbonate-carbon composite, the roasting uses temperature programming method, according to 3-8 to room temperature
DEG C/heating rate of min by room temperature, to 300-700 DEG C, then keeps the temperature 2-5h；Heating rate is fast, temperature and time is longer,
The basic lead carbonate particles size of formation opposite can also increase.
The preparation method of nanometer basic lead carbonate-carbon composite of the present invention, wherein lead described in step (1)
Source is at least one of plumbi nitras, lead acetate, lead chloride and lead citrate, and the solubility of the lead source in water is larger, molten
It is fast to solve speed.
The preparation method of nanometer basic lead carbonate-carbon composite of the present invention, wherein molten described in step (1)
The mass concentration of liquid A is 2.5-9%；The mass concentration of strong base solution described in step (3) is 2.5-9%, above-mentioned mass concentration
In range, the basic lead carbonate of carbon material surface load is uniform, and size is small；Mass concentration is big, the alkali formula of carbon material surface load
Ceruse is more, and unevenly, size is big.
The preparation method of nanometer basic lead carbonate-carbon composite of the present invention, wherein lead described in step (2)
The feed ratio of source and the carbon material is calculated as 0.32-2 with the mass ratio of lead element and the carbon material.
The preparation method of nanometer basic lead carbonate-carbon composite of the present invention, wherein described in step (3)
Strong base solution is at least one of sodium hydroxide solution and potassium hydroxide solution.
The preparation method of nanometer basic lead carbonate-carbon composite of the present invention, wherein the vacuum in step (3)
Drying condition are as follows: drying temperature is 60-80 DEG C, drying time 3-24h；Temperature is too low, the time it is too short will cause drying it is not thorough
Bottom, temperature is high, and the time is long, at high cost.
The preparation method of nanometer basic lead carbonate-carbon composite of the present invention, wherein protected described in step (4)
Shield gas is at least one of argon gas, nitrogen and helium.
The present invention also provides the nanometer basic lead carbonate-carbon composites to exist as lead carbon battery negative electrode active material
Application in lead carbon battery.
The preparation method of nanometer basic lead carbonate-carbon composite of the present invention, principle are as follows: strong base solution with contain
After the lead salt solution mixing of carbon, one layer of unformed substance can be generated and wrap up carbon material；In subsequent high-temperature calcination process, layer
The unformed substance of shape is shrunk to core, forms the nanometer basic lead carbonate of crystal form state；Basic lead carbonate in chemical conversion, (live by chemical conversion
Change, green plate is ripe pole plate by chemical conversion post activation, and the substance on ripe pole plate is active material) during, it will form titanium dioxide
Carbon gas increases utilization rate to increase the porosity of cathode；Spongy lead can be also formed after chemical conversion, improve carbon material sheet
The overpotential of hydrogen evolution of body.
The invention has the advantages that:
(1) nanometer basic lead carbonate-carbon composite prepared by the present invention, as lead carbon battery cathode additive agent, small
The basic lead carbonate of grain can play the role of crystal seed, and the particle of the lead sulfate of formation is small and uniform, so as to preferably prolong
The irreversible sulfation of slow cathode, improves the cycle life of lead carbon battery.Opposite carbon materials are found by test overpotential of hydrogen evolution
Material itself improves 0.1-0.5V, can preferably inhibit evolving hydrogen reaction.
(2) preparation method of nanometer basic lead carbonate-carbon composite of the present invention, by strong base solution and containing described
After the lead source solution mixing of carbon material, then form through high-temperature roasting, it is easy to operate, it is low in cost, to production equipment and production item
Part is not harsh, obtained basic lead carbonate size small (150nm or less) and is evenly dispersed on the surface of carbon material.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of products therefrom in embodiment 1；
Fig. 2 is powder x-ray diffraction (XRD) figure of products therefrom in embodiment 1；
Fig. 3 is scanning electron microscope (SEM) figure of products therefrom in embodiment 2；
Fig. 4 is scanning electron microscope (SEM) figure of the products therefrom in embodiment 3.
Below in conjunction with specific embodiments and the drawings, the invention will be further described.
Specific embodiment
Crystal structure analysis is carried out using X ' Pert PRO type X-ray diffractometer in following embodiment of the present invention, using Cu
Target is as radiation source, maximum power 2.2kW, maximum voltage 60kV, maximum current 55mA.10 °/min of sweep speed, scanning range
10-80°；Using the micro-structure of Hitachi's Hitachi S4700 type field emission scanning electron microscope analysis product.
Embodiment 1
A kind of nanometer of basic lead carbonate-carbon composite by carbon material and is dispersed in receiving for the carbon material surface
Rice basic lead carbonate particles composition, the carbon material are rice hull carbon.
The basic lead carbonate of nanometer described in the present embodiment-carbon composite preparation method, comprising the following steps:
(1) prepared by solution A: 1g plumbi nitras being added in the beaker of 250ml, 40mL deionized water is then added, uses glass
Stick is stirred to plumbi nitras and is completely dissolved, and obtains solution A；
(2) prepared by solution B: 1g rice hull carbon being added in solution A described in step (1), then magnetic agitation 0.5h, obtains
To solution B, the overpotential of hydrogen evolution 1.2V of the rice hull carbon, specific capacitance 220F/g, specific surface area 1850m2/ g, reference electrode are
Mercury/Mercurous sulfate electrode, is platinum electrode to electrode, and electrolyte is the sulfuric acid solution of 1.28g/ml；
(3) precursor preparation: strong base solution is added drop-wise in solution B described in step (2), magnetic agitation 0.5h, vacuum
It filters, solid is put into drying in vacuum oven, drying temperature is 60 DEG C, and drying time is for 24 hours, to obtain presoma, described
Strong base solution is sodium hydroxide solution, the concentration 0.1g/mL of the strong base solution；
(4) prepared by product: presoma described in step (3) being pulverized, is put into tubular type kiln roasting, setting program is such as
Under: initial temperature is 25 DEG C, and heating rate is 3 DEG C/min, and final temperature is 300 DEG C, keeps the temperature 2h, calcination atmosphere is argon gas, so
After be naturally cooling to room temperature, obtain product.
Liberation of hydrogen test: the present embodiment product 0.08g, Kynoar (PVDF) 0.01g and acetylene black 0.01g, in N- are taken
It is uniformly mixed in methyl pyrrolidone (NMP) solvent, slurry is made.The slurry is coated onto titanium sheet, obtains lead charcoal after dry
Electrode；Rice hull carbon is replaced into product, carbon resistance rod is made.Using the lead carbon resistance rod and the carbon resistance rod as working electrode, mercury/sulphur
Sour mercurous is reference electrode, and platinum electrode is to electrode, and the sulfuric acid of 1.28g/ml is electrolyte, and sweeping speed is 5mV/s, tests its liberation of hydrogen
Current potential.Test result shows: the overpotential of hydrogen evolution of carbon improves 0.2V after load nanometer basic lead carbonate, illustrates this nanometer alkali
Formula ceruse is equably supported on after carbon surface the evolving hydrogen reaction that can inhibit carbon surface.
Fig. 1 and Fig. 2 is respectively the SEM figure and XRD diagram of products therefrom in the present embodiment, by Fig. 1 it can be concluded that nanometer alkali formula
The size of ceruse is in 150nm hereinafter, simultaneously it can be concluded that basic lead carbonate is evenly distributed in carbon material surface, by Fig. 2
It can be concluded that the substance of load is basic lead carbonate.
Embodiment 2
A kind of nanometer of basic lead carbonate-carbon composite by carbon material and is dispersed in receiving for the carbon material surface
Rice basic lead carbonate particles composition, the carbon material are coconut carbon.
The basic lead carbonate of nanometer described in the present embodiment-carbon composite preparation method, comprising the following steps:
(1) prepared by solution A: 4g lead chloride being added in the beaker of 250ml, 40mL deionized water is then added, uses glass
Stick is stirred to lead chloride and is completely dissolved, and obtains solution A；
(2) prepared by solution B: 2g coconut carbon being added in solution A described in step (1), then magnetic agitation 1h, obtains
Solution B, the overpotential of hydrogen evolution 1.15V of the coconut carbon, specific capacitance 202F/g, specific surface area 1678m2/ g, reference electrode be mercury/
Mercurous sulfate electrode, is platinum electrode to electrode, and electrolyte is the sulfuric acid solution of 1.28g/ml；
(3) precursor preparation: strong base solution is added drop-wise in solution B described in step (2), magnetic agitation 0.5h, vacuum
It filters, solid is put into drying in vacuum oven, drying temperature is 80 DEG C, and drying time 12h obtains presoma, described
Strong base solution is potassium hydroxide solution, the concentration 0.1g/mL of the strong base solution；
(4) prepared by product: presoma described in step (3) being pulverized, is put into tubular type kiln roasting, setting program is such as
Under: initial temperature is 25 DEG C, and heating rate is 5 DEG C/min, and final temperature is 400 DEG C, keeps the temperature 2h, calcination atmosphere is nitrogen, so
After be naturally cooling to room temperature, obtain product.
Liberation of hydrogen test: taking the present embodiment product 0.08g, PVDF0.01g and acetylene black 0.01g, mixes in nmp solvent equal
It is even, slurry is made.The slurry is coated onto titanium sheet, obtains lead carbon resistance rod after dry；Coconut carbon is replaced into product, charcoal electricity is made
Pole.Using the lead carbon resistance rod and the carbon resistance rod as working electrode, mercury/mereurous sulfate is reference electrode, and platinum electrode is to electricity
Pole, the sulfuric acid of 1.28g/ml are electrolyte, and sweeping speed is 5mV/s, tests its hydrogen-evolution overpotential.Test result shows: load nanometer alkali
The overpotential of hydrogen evolution of carbon improves 0.21V after formula ceruse, illustrates that this nanometer basic lead carbonate is equably supported on carbon surface
It can inhibit the evolving hydrogen reaction of carbon surface afterwards.
Fig. 3 be the present embodiment in products therefrom SEM figure, by Fig. 3 it can be concluded that the size of basic lead carbonate 150nm with
Under, while it can be concluded that basic lead carbonate is evenly distributed in carbon material surface.
Embodiment 3
A kind of nanometer of basic lead carbonate-carbon composite by carbon material and is dispersed in receiving for the carbon material surface
Rice basic lead carbonate particles composition, the carbon material are coconut carbon.
The basic lead carbonate of nanometer described in the present embodiment-carbon composite preparation method, comprising the following steps:
(1) prepared by solution A: 2g lead acetate being added in the beaker of 250ml, 40mL deionized water is then added, uses glass
Stick is stirred to lead acetate and is completely dissolved, and obtains solution A；
(2) prepared by solution B: 1g coconut carbon being added in solution A described in step (1), then magnetic agitation 1h, obtains
Solution B, the overpotential of hydrogen evolution 1.15V of the coconut carbon, specific capacitance 202F/g, specific surface area 1678m2/ g, reference electrode be mercury/
Mercurous sulfate electrode, is platinum electrode to electrode, and electrolyte is the sulfuric acid solution of 1.28g/ml；
(3) precursor preparation: strong base solution is added drop-wise in solution B described in step (2), magnetic agitation 0.5h, vacuum
It filters, solid is put into drying in vacuum oven, drying temperature is 80 DEG C, and drying time 12h obtains presoma, described
Strong base solution is potassium hydroxide solution, the concentration 0.05g/mL of the strong base solution；
(4) prepared by product: presoma described in step (3) being pulverized, is put into tubular type kiln roasting, setting program is such as
Under: initial temperature is 25 DEG C, and heating rate is 8 DEG C/min, and final temperature is 400 DEG C, keeps the temperature 2h, calcination atmosphere is nitrogen, so
After be naturally cooling to room temperature, obtain product.
Liberation of hydrogen test: taking the present embodiment product 0.08g, PVDF0.01g and acetylene black 0.01g, mixes in nmp solvent equal
It is even, slurry is made.The slurry is coated onto titanium sheet, obtains lead carbon resistance rod after dry；Coconut carbon is replaced into product, charcoal electricity is made
Pole.Using the lead carbon resistance rod and the carbon resistance rod as working electrode, mercury/mereurous sulfate is reference electrode, and platinum electrode is to electricity
Pole, the sulfuric acid of 1.28g/ml are electrolyte, and sweeping speed is 5mV/s, tests its hydrogen-evolution overpotential.Test result shows: load nanometer alkali
The overpotential of hydrogen evolution of carbon improves 0.19V after formula ceruse, illustrates that this nanometer basic lead carbonate is equably supported on carbon surface
It can inhibit the evolving hydrogen reaction of carbon surface afterwards.
Fig. 4 be the present embodiment in products therefrom SEM figure, by Fig. 4 it can be concluded that the size of basic lead carbonate 150nm with
Under, while it can be concluded that basic lead carbonate is evenly distributed in carbon material surface.
Embodiment 4
A kind of nanometer of basic lead carbonate-carbon composite by carbon material and is dispersed in receiving for the carbon material surface
Rice basic lead carbonate particles composition, the carbon material are rice hull carbon.
The basic lead carbonate of nanometer described in the present embodiment-carbon composite preparation method, comprising the following steps:
(1) prepared by solution A: 2g lead citrate being added in the beaker of 250ml, 40mL deionized water is then added, uses glass
Glass stick, which is stirred to lead citrate, to be completely dissolved, and solution A is obtained；
(2) prepared by solution B: 1g rice hull carbon being added in solution A described in step (1), then magnetic agitation 1h, obtains
Solution B, the overpotential of hydrogen evolution 1.2V of the rice hull carbon, specific capacitance 220F/g, specific surface area 1850m2/ g, reference electrode be mercury/
Mercurous sulfate electrode, is platinum electrode to electrode, and electrolyte is the sulfuric acid solution of 1.28g/ml；
(3) precursor preparation: strong base solution is added drop-wise in solution B described in step (2), magnetic agitation 0.5h, vacuum
It filters, solid is put into drying in vacuum oven, drying temperature is 60 DEG C, and drying time 12h obtains presoma, described
Strong base solution is sodium hydroxide solution, the concentration 0.05g/mL of the strong base solution；
(4) prepared by product: presoma described in step (3) being pulverized, is put into tubular type kiln roasting, setting program is such as
Under: initial temperature is 25 DEG C, and heating rate is 8 DEG C/min, and final temperature is 400 DEG C, keeps the temperature 2h, calcination atmosphere is nitrogen, so
After be naturally cooling to room temperature, obtain product.
Liberation of hydrogen test: taking the present embodiment product 0.08g, PVDF0.01g and acetylene black 0.01g, mixes in nmp solvent equal
It is even, slurry is made.The slurry is coated onto titanium sheet, obtains lead carbon resistance rod after dry；Rice hull carbon is replaced into product, charcoal electricity is made
Pole.Using the lead carbon resistance rod and the carbon resistance rod as working electrode, mercury/mereurous sulfate is reference electrode, and platinum electrode is to electricity
Pole, the sulfuric acid of 1.28g/ml are electrolyte, and sweeping speed is 5mV/s, tests its hydrogen-evolution overpotential.Test result shows: load nanometer alkali
The overpotential of hydrogen evolution of carbon improves 0.2V after formula ceruse, after illustrating that this nanometer basic lead carbonate is equably supported on carbon surface
It can inhibit the evolving hydrogen reaction of carbon surface.
Embodiment 5
A kind of nanometer of basic lead carbonate-carbon composite by carbon material and is dispersed in receiving for the carbon material surface
Rice basic lead carbonate particles composition, the carbon material are graphene.
The basic lead carbonate of nanometer described in the present embodiment-carbon composite preparation method, comprising the following steps:
(1) prepared by solution A: 2g plumbi nitras being added in the beaker of 250ml, 40mL deionized water is then added, uses glass
Stick is stirred to plumbi nitras and is completely dissolved, and obtains solution A；
(2) prepared by solution B: 1g graphene being added in solution A described in step (1), then magnetic agitation 1h, obtains
Solution B, the overpotential of hydrogen evolution 1.1V of the graphene, specific capacitance 240F/g, specific surface area 2250m2/ g, reference electrode be mercury/
Mercurous sulfate electrode, is platinum electrode to electrode, and electrolyte is the sulfuric acid solution of 1.28g/ml；
(3) precursor preparation: strong base solution is added drop-wise in solution B described in step (2), magnetic agitation 0.5h, vacuum
It filters, solid is put into drying in vacuum oven, drying temperature is 60 DEG C, and drying time 12h obtains presoma, described
Strong base solution is sodium hydroxide solution, the concentration 0.05g/mL of the strong base solution；
(4) prepared by product: presoma described in step (3) being pulverized, is put into tubular type kiln roasting, setting program is such as
Under: initial temperature is 25 DEG C, and heating rate is 5 DEG C/min, and final temperature is 700 DEG C, keeps the temperature 2h, calcination atmosphere is helium, so
After be naturally cooling to room temperature, obtain product.
Liberation of hydrogen test: taking the present embodiment product 0.08g, PVDF0.01g and acetylene black 0.01g, mixes in nmp solvent equal
It is even, slurry is made.The slurry is coated onto titanium sheet, obtains lead carbon resistance rod after dry；Graphene is replaced into product, charcoal electricity is made
Pole.Using the lead carbon resistance rod and the carbon resistance rod as working electrode, mercury/mereurous sulfate is reference electrode, and platinum electrode is to electricity
Pole, the sulfuric acid of 1.28g/ml are electrolyte, and sweeping speed is 5mV/s, tests its hydrogen-evolution overpotential.Test result shows: load nanometer alkali
The overpotential of hydrogen evolution of carbon improves 0.2V after formula ceruse, after illustrating that this nanometer basic lead carbonate is equably supported on carbon surface
It can inhibit the evolving hydrogen reaction of carbon surface.
Embodiment described above only describe the preferred embodiments of the invention, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made should all be fallen into the protection scope that claims of the present invention determines.
Claims (10)
1. a kind of nanometer of basic lead carbonate-carbon composite, it is characterised in that: by carbon material and be dispersed in the carbon material
The nanometer basic lead carbonate particles on surface form, and the nanometer basic lead carbonate particles are in 150nm or less.
2. according to claim 1 nanometer of basic lead carbonate-carbon composite, it is characterised in that: the carbon material is coconut palm
One of shell carbon, rice hull carbon and graphene or two or more mixtures.
3. of any of claims 1 or 2 nanometer of basic lead carbonate-carbon composite preparation method, it is characterised in that: including with
Lower step:
(1) prepared by solution A: lead source being added in beaker, deionized water is then added, stirring is completely dissolved to the lead source, obtains
To solution A, the mass concentration of the solution A is 2.5-10%；
(2) prepared by solution B: carbon material being added in solution A described in step (1), then magnetic agitation 0.5-1h, so that lead
Ion and the carbon material are evenly dispersed in deionized water, obtain solution B, the feed ratio in the lead source and the carbon material
0.3-5 is calculated as with the mass ratio of lead element and the carbon material；
(3) precursor preparation: strong base solution being added drop-wise in solution B described in step (2), magnetic agitation 0.5-1h, and vacuum is taken out
Solid is put into drying in vacuum oven by filter, obtains presoma, and the mass concentration of the strong base solution is 2.5-10%；
(4) prepared by product: presoma described in step (3) being pulverized, roasts in protective atmosphere, is then naturally cooling to
Room temperature obtains product nano basic lead carbonate-carbon composite, and the roasting uses temperature programming method, according to 3-8 DEG C/min
Heating rate by room temperature to 300-700 DEG C, then keep the temperature 2-5h.
4. according to claim 3 nanometer of basic lead carbonate-carbon composite preparation method, it is characterised in that: step
(1) lead source described in is at least one of plumbi nitras, lead acetate, lead chloride and lead citrate.
5. according to claim 3 nanometer of basic lead carbonate-carbon composite preparation method, it is characterised in that: step
(1) mass concentration of solution A described in is 2.5-9%；The mass concentration of strong base solution described in step (3) is 2.5-9%.
6. according to claim 3 nanometer of basic lead carbonate-carbon composite preparation method, it is characterised in that: step
(2) feed ratio of lead source described in and the carbon material is calculated as 0.32-2 with the mass ratio of lead element and the carbon material.
7. according to claim 3 nanometer of basic lead carbonate-carbon composite preparation method, it is characterised in that: step
(3) strong base solution described in is at least one of sodium hydroxide solution and potassium hydroxide solution.
8. according to claim 3 nanometer of basic lead carbonate-carbon composite preparation method, it is characterised in that: step
(3) the vacuum drying condition in are as follows: drying temperature is 60-80 DEG C, drying time 3-24h.
9. according to claim 3 nanometer of basic lead carbonate-carbon composite preparation method, it is characterised in that: step
(4) protection gas described in is at least one of argon gas, nitrogen and helium.
10. as claimed in claim 1 or 2 nanometer of basic lead carbonate-carbon composite is as lead carbon battery negative electrode active material in lead
Application in carbon battery.
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| CN103035894A (en) * | 2012-12-19 | 2013-04-10 | 浙江工业大学 | Method for preparing composite modified material for lead carbon superbattery |
| CN106531972A (en) * | 2016-08-17 | 2017-03-22 | 重庆大学 | Preparation method of lead-graphene composite material for lead-carbon battery |
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