CN109411734A - A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous - Google Patents
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous Download PDFInfo
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Abstract
The present invention relates to negative plates of lead carbon battery and preparation method thereof, more particularly to a kind of preparation method of lead carbon composite that lead carbon battery cathode is classifying porous, by preparing the phenolic resin colloid added with pore-foaming agent, then the classifying porous lead carbon composite that lead is modified, and successively carbonization-activation is needed after removing pore-foaming agent is carried out using soluble lead salt.The classifying porous lead carbon composite that the present invention obtains is carried out by chelatropic reaction, and the compatibility of lead phase and carbon phase is advantageously accounted for, and is improved the charge-discharge performance of lead carbon battery and is prolonged its service life.
Description
Technical field
The present invention relates to negative plates of lead carbon battery and preparation method thereof, and in particular to a kind of lead carbon battery cathode classification is more
The preparation method of the lead carbon composite in hole.
Background technique
With electric car, the rapid development of the electric vehicles such as electric bicycle, lead-acid accumulator due to its technical maturity,
Performance is stable, highly-safe, cheap receives the favor in market, at present lead-acid accumulator in electric bicycle in the market
Occupation rate reaches 95% or more.The characteristics of due to lead-acid accumulator itself, charging current cannot be excessive, is typically chosen charging electricity
Stream is the 10-30% of rated capacity, and charging is had to fully charged every time, is just conducive to extend its service life in this way, is caused
Battery is set to need the charging of long period.But in practical applications, being limited battery by this condition often will appear charge less
Operation under electricity condition, charge less electricity condition make negative electrode active material performance failure using the process that can accelerate cathode sulfation,
And then entire battery is caused to be scrapped.Meanwhile application requirement battery of the lead-acid accumulator on electric car, electric bicycle has
Stronger quick charge ability to accept, so as to shorten the charging time.It, not only can be with research shows that add carbon material in negative plate
The charge acceptance for improving cell negative plate, can also effectively slow down the sulfation process of cathode, extend the circulation longevity of battery
Life, referring to Journal of Power Sources, 1997,64,147-152.The article that D.Pavlov was delivered in 2009, report
The mechanism of action of carbon (EAC) in road lead-acid battery cathode plate charge and discharge process with electro-chemical activity.
Lead carbon battery has safety identical with conventional lead acid, cheapness and stability.In addition, it has and super capacitor
The longer cycle life of device and higher specific power.Porous carbon materials are added in negative plate can extend high magnification partial state of charge
Cycle life under state (HRPSoC) operation.Meanwhile the research of carbon mechanism of action promotes lead carbon battery in energy storage field
Practical application, carbonaceous additive primarily serves the effect for providing capacitive buffer, conductive network, so as to improve electrochemical kinetics scholarship and moral conduct
For.However, serious problems also occurs in carbonaceous additive, such as improves liberation of hydrogen rate and reduce negative electrode active material (lead sponge) and carbon
Connection between material.In addition, the hydrogen generated can be such that carbon particle separates with lead, lead to the destruction of anode plate stability.
Lead overpotential of hydrogen evolution with higher can effectively inhibit evolving hydrogen reaction after forming lead carbon complex.Recently, lead carbon is compound
The additive that material is used as lead carbon battery has many embodiments.
Xue et al. is prepared for a kind of carbon/lead composite material by calcining lead citrate precursor；Ma et al. has obtained a stone
Black alkene/sulfuric acid lead composite material is by the way that graphene to be immersed in lead acetate and sulfuric acid solution；Hong et al. passes through ULTRASONIC ABSORPTION
Nano level modified absorbent charcoal composite material is prepared for chemical precipitation；Tong et al. has prepared an one kind and has contained plumbous work
Property Carbon Materials；Wang et al., which discloses lead, can be electrodeposited into nanoscale carbon pores formation lead carbon complex, apply it to lead carbon electricity
Chi Zhong can extend cycle life.
At present the carbon material of lead carbon battery primarily directed to supercapacitor active carbon material, with realize its height than electricity
Holding is target.But since carbon material can bring serious liberation of hydrogen problem and lead carbon two-phase interface is incompatible asks in lead carbon battery
Topic solves the irreversible sulfation of cathode and asks so need to start with from lead carbon composite to prepare high performance lead carbon battery
Topic and cathode liberation of hydrogen and lead to the failure of battery, improve battery cycle life and high-rate charge-discharge capability.
Summary of the invention
In view of the above problems, the present invention proposes a kind of preparation side of lead carbon composite that lead carbon battery cathode is classifying porous
Method, it is easy to operate, novel, obtain the negative plate electrochemical performance for lead carbon battery, two object phase good compatibility of lead carbon.
In order to achieve the above object, the present invention is achieved through the following technical solutions: a kind of lead carbon battery cathode is classifying porous
Lead carbon composite preparation method, comprising the following steps:
(1) by ammonium hydroxide, alcohols and water mix, stir 40-70min after resorcinol is added, continue stir 20-40min, then plus
Enter formaldehyde and pore-foaming agent, continuation stirs 20-26h at 20-35 DEG C, obtains phenolic resin colloid；The ammonium hydroxide, alcohols and water
Volume ratio is 1:(70-80): the mass ratio of (100-200), the resorcinol and formaldehyde is 1:(1-2).
(2) down in the phenolic resin colloid after soluble lead salt being dissolved in water, 6-8h is stirred at 20-30 DEG C,
It is washed 2-4 times respectively after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(3) the modified phenolic resin of lead is subjected to Soxhlet extraction by solvent of acetone, the time is 6-7 hours, removes pore-foaming agent, obtains
To preliminary composite；
(4) preliminary composite is carbonized under the protection of nitrogen or inert gas, with the heating rate of 2-5 DEG C/min by room temperature
2-3h is kept the temperature after rising to 600-800 DEG C, obtains secondary composite material；
(5) secondary composite material and potassium hydroxide are mixed, is activated under the protection of nitrogen or inert gas, with 2-5 DEG C/min
Heating rate rise to 600-800 DEG C after keep the temperature 2-3h, obtain classifying porous lead carbon composite；The secondary composite material
Mass ratio with potassium hydroxide is 1:(2-6).
Preferably, the alcohols is one of methanol, ethyl alcohol and ethylene glycol or a variety of.
Preferably, the soluble lead salt is one of plumbi nitras, lead acetate and lead chloride or a variety of, the solubility
The mass fraction of lead salt is the 0.05-0.6% of the gross mass of the phenolic resin colloid disperse system.
Preferably, the pore-foaming agent is one of toluene, n-hexane, urea and calcium oxide or a variety of.
It is further preferred that the pore-foaming agent is toluene, mass fraction is the total matter of mixed solution before forming colloid
The 0.1-0.5% of amount.
Preferably, the stirring operation in preparation process is all made of magnetic agitation.
The classifying porous lead carbon composite as lead carbon battery negative electrode material application method the following steps are included:
(1) the lead carbon composite is mixed with lead powder 1:20-99 in mass ratio, is added after staple fiber and additive and sulfuric acid
Solution mixing, be uniformly mixing to obtain paste, paste be applied on negative electrode grid, it is two-sided to strike off, through rolling, pickling, solidification,
Cathode green plate is made after drying；
(2) by tank formation or internal formation process route, lead carbon battery is made；
Tank formation process route: cathode life is polarized to, redrying, obtains the ripe pole plate of cathode that can be used for lead carbon battery.Again
By its with after chemical conversion the ripe pole plate of anode and partition be assembled into battery, sulfuric acid electrolyte is added, it is electro-active through charge and discharge, lead carbon is made
Finished battery.
Internal formation process route: cathode green plate and positive green plate are subjected to battery assembly, sulfuric acid electrolyte, warp is added
Specific charge and discharge system activation, is made lead carbon battery finished product.
It is further preferred that the mass ratio of the lead carbon composite and lead powder is 1:99 to 3:97.
Preferably, staple fiber is one of polypropylene fibre, polyester fiber and acrylic fiber or a variety of, length 0.5-
2mm。
It is further preferred that the additive is one of barium sulfate, acetylene black, carbon black and humic acid or a variety of.
Of the invention is preferentially:
(1) the classifying porous lead carbon composite that the present invention obtains is carried out by chelatropic reaction, advantageously accounts for lead phase
With the compatibility of carbon phase, improves the charge-discharge performance of lead carbon battery and prolong its service life.
(2) use of pore-foaming agent is conducive to generate more micropores, increases the specific capacitance of lead carbon composite.
(3) it is used in combination using pore-foaming agent toluene and activator potassium hydroxide, is conducive to the cyclicity for promoting lead carbon battery
Energy, high rate performance and capacity.
(4) the classifying porous lead carbon complex that the present invention obtains is applied to the cathode of lead carbon battery, can effectively inhibit lead
Carbon battery cathode liberation of hydrogen and irreversible sulfation.
Detailed description of the invention
Attached drawing 1 is the SEM of the phenolic resin base carbon material (PRC) after carbonization-activation；
Attached drawing 2 is the SEM for the classifying porous lead carbon composite (Pb/PRC) that embodiment 1 obtains；
Attached drawing 3 is that phenolic resin base carbon material (PRC) after carbonization-activation and the obtained classifying porous lead carbon of embodiment 1 are compound
The XRD of material (Pb/PRC)；
Attached drawing 4 is the BET for the classifying porous lead carbon composite (Pb/PRC) that embodiment 1 obtains；
Attached drawing 5 is conventional lead acid battery (blank) and joined the battery of phenolic resin base carbon material (PRC) and joined reality
Apply the cycle performance comparison diagram of the lead carbon battery for the classifying porous lead carbon composite (Pb/PRC) that example 1 obtains.
Specific embodiment
This specific implementation method is only explanation of the invention, is not limitation of the present invention.Those skilled in the art
Member's any change made after having read specification of the invention, as long as within the scope of the claims, it all will be by
To the protection of Patent Law.
Embodiment 1:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.42g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.56g formaldehyde and above-mentioned mixed liquor gross mass 0.2% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) nitric acid is added in the phenolic resin colloid by the proportion for being 0.25% in the mass fraction in phenolic resin colloid
Lead solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 700 DEG C with the heating rate of 3 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:4 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 3
DEG C/heating rate of min keeps the temperature 3h after rising to 700 DEG C, finally obtain classifying porous lead carbon composite.
Embodiment 2:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.42g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.56g formaldehyde and above-mentioned mixed liquor gross mass 0.2% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) nitric acid is added in the phenolic resin colloid by the proportion for being 0.25% in the mass fraction in phenolic resin colloid
Lead solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains after vacuum oven is dry
The modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 700 DEG C with the heating rate of 5 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:2 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 5
DEG C/heating rate of min keeps the temperature 3h after rising to 700 DEG C, finally obtain classifying porous lead carbon composite.
Embodiment 3:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.42g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.56g formaldehyde and above-mentioned mixed liquor gross mass 0.3% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) nitric acid is added in the phenolic resin colloid by the proportion for being 0.25% in the mass fraction in phenolic resin colloid
Lead solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 800 DEG C with the heating rate of 3 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:4 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 3
DEG C/heating rate of min keeps the temperature 3h after rising to 800 DEG C, finally obtain classifying porous lead carbon composite.
Embodiment 4:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.42g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.56g formaldehyde and above-mentioned mixed liquor gross mass 0.2% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) plumbi nitras is added in the phenolic resin colloid by the proportion for being 0.5% in the mass fraction in phenolic resin colloid
Solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 800 DEG C with the heating rate of 3 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:4 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 3
DEG C/heating rate of min keeps the temperature 3h after rising to 800 DEG C, finally obtain classifying porous lead carbon composite.
Embodiment 5:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.5g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.5g formaldehyde and above-mentioned mixed liquor gross mass 0.2% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) nitric acid is added in the phenolic resin colloid by the proportion for being 0.25% in the mass fraction in phenolic resin colloid
Lead solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 700 DEG C with the heating rate of 3 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:6 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 3
DEG C/heating rate of min keeps the temperature 3h after rising to 700 DEG C, finally obtain classifying porous lead carbon composite.
Embodiment 6:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 120ml water are mixed, 0.42g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.56g formaldehyde and above-mentioned mixed liquor gross mass 0.2% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) nitric acid is added in the phenolic resin colloid by the proportion for being 0.25% in the mass fraction in phenolic resin colloid
Lead solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 700 DEG C with the heating rate of 3 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:4 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 3
DEG C/heating rate of min keeps the temperature 3h after rising to 700 DEG C, finally obtain classifying porous lead carbon composite.
Embodiment 7:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.42g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.56g formaldehyde and above-mentioned mixed liquor gross mass 0.5% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) nitric acid is added in the phenolic resin colloid by the proportion for being 0.25% in the mass fraction in phenolic resin colloid
Lead solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 700 DEG C with the heating rate of 3 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:4 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 3
DEG C/heating rate of min keeps the temperature 3h after rising to 700 DEG C, finally obtain classifying porous lead carbon composite.
Embodiment 8:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.42g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.56g formaldehyde and above-mentioned mixed liquor gross mass 0.2% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) nitric acid is added in the phenolic resin colloid by the proportion for being 0.25% in the mass fraction in phenolic resin colloid
Lead solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 600 DEG C with the heating rate of 5 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:4 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 5
DEG C/heating rate of min keeps the temperature 3h after rising to 600 DEG C, finally obtain classifying porous lead carbon composite.
Comparative example 1:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.42g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.56g formaldehyde and above-mentioned mixed liquor gross mass 0.2% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) nitric acid is added in the phenolic resin colloid by the proportion for being 0.25% in the mass fraction in phenolic resin colloid
Lead solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 700 DEG C with the heating rate of 3 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:8 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 3
DEG C/heating rate of min keeps the temperature 3h after rising to 700 DEG C, finally obtain classifying porous lead carbon composite.
Comparative example 2:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.42g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.56g formaldehyde and above-mentioned mixed liquor gross mass 0.2% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) nitric acid is added in the phenolic resin colloid by the proportion for being 0.25% in the mass fraction in phenolic resin colloid
Lead solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains after vacuum oven is dry
The modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 700 DEG C with the heating rate of 7 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:4 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 7
DEG C/heating rate of min keeps the temperature 3h after rising to 700 DEG C, finally obtain classifying porous lead carbon composite.
Comparative example 3:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.42g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.56g formaldehyde and above-mentioned mixed liquor gross mass 0.05% is then added, and continues
It is stirred at 30 DEG C for 24 hours, obtains phenolic resin colloid；
(2) nitric acid is added in the phenolic resin colloid by the proportion for being 0.25% in the mass fraction in phenolic resin colloid
Lead solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 900 DEG C with the heating rate of 3 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:4 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 3
DEG C/heating rate of min keeps the temperature 3h after rising to 900 DEG C, finally obtain classifying porous lead carbon composite.
Comparative example 4:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.42g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.56g formaldehyde and above-mentioned mixed liquor gross mass 0.2% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) by the proportion for being 1% in the mass fraction in phenolic resin colloid, that plumbi nitras is added in the phenolic resin colloid is molten
Liquid stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(3) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(4) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 800 DEG C with the heating rate of 3 DEG C/min,
Obtain secondary composite material；
(5) in mass ratio it is that 1:4 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 3
DEG C/heating rate of min keeps the temperature 3h after rising to 800 DEG C, finally obtain classifying porous lead carbon composite.
Comparative example 5:
A kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which comprises the following steps:
(1) 0.8ml ammonium hydroxide, 60ml ethyl alcohol and 160ml water are mixed, 0.6g isophthalic is added after magnetic agitation 60min at 25 DEG C
Diphenol continues magnetic agitation 30min, and the toluene of 0.4g formaldehyde and above-mentioned mixed liquor gross mass 0.2% is then added, and continues 30
It is stirred at DEG C for 24 hours, obtains phenolic resin colloid；
(2) nitric acid is added in the phenolic resin colloid by the proportion for being 0.25% in the mass fraction in phenolic resin colloid
Lead solution stirs 7h at 20 DEG C, is washed respectively 3 times after centrifuge separation with ethyl alcohol and water, obtains the modified phenolic resin of lead；
(1) by the modified phenolic resin of lead, Soxhlet extraction, time 6h remove toluene, obtain preliminary composite in acetone；
(2) preliminary composite is carbonized under the protection of nitrogen, keeps the temperature 3h after rising to 700 DEG C with the heating rate of 3 DEG C/min,
Obtain secondary composite material；
(3) in mass ratio it is that 1:4 is mixed by secondary composite material and potassium hydroxide, is activated under the protection of nitrogen, equally with 3
DEG C/heating rate of min keeps the temperature 3h after rising to 700 DEG C, finally obtain classifying porous lead carbon composite.
The classifying porous lead carbon composite for respectively obtaining embodiment 1-5 and comparative example 1-5 is prepared into lead carbon battery
Battery module is used for after active cathode plate, the application method as lead carbon battery negative electrode material to be as follows:
(1) obtained lead carbon composite is mixed with lead powder 1:99 in mass ratio, after staple fiber, barium sulfate and humic acid is added
It is mixed with sulfuric acid solution, is uniformly mixing to obtain paste, paste is applied on grid, it is two-sided to strike off, through rolling, pickling, consolidate
Obtained cathode green plate after changing, being dry；Wherein, staple fiber is the mixture of 1mm polypropylene and 1mm acrylic fiber；
(2) by tank formation process route, lead carbon battery, tank formation process route is made are as follows: cathode life is polarized to, is secondary dry
It is dry, obtain the ripe pole plate of cathode that can be used for lead carbon battery.Again by its with after chemical conversion the ripe pole plate of anode and partition be assembled into battery,
Sulfuric acid electrolyte is added, it is electro-active through charge and discharge, lead carbon battery finished product is made.
The classifying porous lead carbon composite that embodiment 6-8 is obtained is used for after being prepared into lead carbon battery active cathode plate
Battery module, the application method as lead carbon battery negative electrode material are as follows:
(1) obtained lead carbon composite is mixed with lead powder 3:97 in mass ratio, staple fiber, barium sulfate, humic acid, carbon is added
It is mixed after black with sulfuric acid solution, is uniformly mixing to obtain paste, paste is applied on grid, it is two-sided to strike off, it rolled, soaked
Cathode green plate is made after acid, solidification, drying；Wherein, staple fiber is 1mm polypropylene fibre, 1mm acrylic fiber and 2mm polyester
The mixture of fiber；
(2) by internal formation process route, lead carbon battery is made, internal formation process route: by cathode green plate and the raw pole of anode
Plate carries out battery assembly, and sulfuric acid electrolyte is added, and activates through specific charge and discharge system, lead carbon battery finished product is made.
To embodiment 1-5, classifying porous lead carbon composite and load the activity prepared with it that comparative example 1-5 is obtained
The lead carbon battery finished product of cell negative plate is tested for the property, and obtains following result；
Such as attached drawing 1, shown in 2,3,4,5, the SEM for the classifying porous lead carbon composite that embodiment 1 obtains is shown as 200-
The nanosphere of 250nm, XRD spectrum Pb/PRC go out peak position and meet Pb (JCPDS 04-0686) and PbO (JCPDS 05-0561),
BET shows that its specific surface area is 530cm3/ g, pore-size distribution is mainly in 1-2nm, 2-10nm and 60-70nm；Battery pack is in high power
Under the negative charge state of rate part, the cycle performance measured is 18000 circles and 100mAh/g.
Comparative example 1 changes the mass ratio of secondary composite material and potassium hydroxide with respect to embodiment 1, joined excessive hydrogen
Potassium oxide finds that excessive potassium hydroxide will lead to the ratio of battery macropore and account for leading, and mesoporous ratio strongly reduces, battery
Cycle performance judgment criteria codetermined by mesoporous and macropore, therefore it is poor to result in comparative example cycle performance of battery.
Comparative example 2 changes heating rate with respect to embodiment 2, and after discovery heating rate is too fast, being carbonized not occurs in comparative example 2
Uniform phenomenon, the volume of activation for also resulting in potassium hydroxide is less, and specific surface area only has 250cm3/g。
The content and the high-temperature temperature after heating that the opposite embodiment 3 of comparative example 3 changes pore-foaming agent toluene, embodiment 3
Obtained battery specific capacity is 100 mAh g-1, after reducing toluene level, the battery specific capacity that comparative example 3 obtains is 60 mAh
g-1, this is seldom related with the micropore that a small amount of toluene generates, and leads to specific capacity also very little；And high-temperature temperature it is higher when, lead carbon is multiple
The degree of graphitization of condensation material also will increase, and cause the specific surface area of material that can reduce.
Comparative example 4 increases the content of soluble lead salt with respect to embodiment 4, and phenolic resin colloid starts to gather in comparative example 4
It is heavy, cause the chelatropic reaction of lead ion and phenolic resin to be difficult to occur, meanwhile, there is the uneven situation of dispersion in lead ion.
Comparative example 5 changes the proportion of resorcinol and formaldehyde with respect to embodiment 5, and different shape occurs in comparative example 5
Nanosphere, and homogeneity is very poor.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method for the lead carbon composite that lead carbon battery cathode is classifying porous, which is characterized in that including following step
It is rapid:
Ammonium hydroxide, alcohols and water are mixed, resorcinol is added after stirring 40-70min, continues to stir 20-40min, then be added
Formaldehyde and pore-foaming agent, continuation stir 20-26h at 20-35 DEG C, obtain phenolic resin colloid；The body of the ammonium hydroxide, alcohols and water
Product ratio is 1:(70-80): the mass ratio of (100-200), the resorcinol and formaldehyde is 1:(1-2)；
Down in the phenolic resin colloid after soluble lead salt is dissolved in water, 6-8h is stirred at 20-30 DEG C, is centrifugated
It is washed 2-4 times respectively with ethyl alcohol and water afterwards, obtains the modified phenolic resin of lead；
The modified phenolic resin of lead is subjected to Soxhlet extraction by solvent of acetone, the time is 6-7 hours, removes pore-foaming agent, obtains
Preliminary composite；
Preliminary composite is carbonized under the protection of nitrogen or inert gas, with the heating rate of 2-5 DEG C/min by room temperature liter
2-3h is kept the temperature after to 600-800 DEG C, obtains secondary composite material；
Secondary composite material and potassium hydroxide are mixed, activated under the protection of nitrogen or inert gas, with the liter of 2-5 DEG C/min
Warm rate keeps the temperature 2-3h after rising to 600-800 DEG C, obtains classifying porous lead carbon composite；The secondary composite material and hydrogen
The mass ratio of potassium oxide is 1:(2-6).
2. a kind of preparation method of the classifying porous lead carbon composite of lead carbon battery cathode according to claim 1,
Be characterized in that: the alcohols is one of methanol, ethyl alcohol and ethylene glycol or a variety of.
3. a kind of preparation method of the classifying porous lead carbon composite of lead carbon battery cathode according to claim 1,
Be characterized in that: the solubility lead salt is one of plumbi nitras, lead acetate and lead chloride or a variety of, the solubility lead salt
Mass fraction is the 0.05-0.6% of the phenolic resin colloid disperse system gross mass.
4. a kind of preparation method of the classifying porous lead carbon composite of lead carbon battery cathode according to claim 1,
Be characterized in that: the pore-foaming agent is one of toluene, n-hexane, urea and calcium oxide or a variety of.
5. a kind of preparation method of the classifying porous lead carbon composite of lead carbon battery cathode according to claim 1,
Be characterized in that: the pore-foaming agent is toluene, mass fraction 0.1-0.5%.
6. a kind of preparation method of the classifying porous lead carbon composite of lead carbon battery cathode according to claim 1,
Be characterized in that: the stirring is magnetic agitation.
7. a kind of application side of classifying porous lead carbon composite as described in claim 1 as lead carbon battery negative electrode material
Method, which comprises the following steps:
By the lead carbon composite and lead powder 1:(20-99 in mass ratio) it mixes, it is added after staple fiber and additive and sulfuric acid
Solution mixing, be uniformly mixing to obtain paste, paste be applied on negative electrode grid, it is two-sided to strike off, through rolling, pickling, solidification,
Cathode green plate is made after drying；
By tank formation or internal formation process route, lead carbon battery is made；
Tank formation process route: cathode life being polarized to, redrying, obtain the ripe pole plate of cathode that can be used for lead carbon battery, then
By its with after chemical conversion the ripe pole plate of anode and partition be assembled into battery, sulfuric acid electrolyte is added, it is electro-active through charge and discharge, lead carbon is made
Finished battery；
Internal formation process route: cathode green plate and positive green plate are subjected to battery assembly, sulfuric acid electrolyte is added, through specific
The activation of charge and discharge system, is made lead carbon battery finished product.
8. application of the classifying porous lead carbon composite of one kind according to claim 7 as lead carbon battery negative electrode material
Method, it is characterised in that: the mass ratio of the lead carbon composite and lead powder is 1:99 to 3:97.
9. application of the classifying porous lead carbon composite of one kind according to claim 7 as lead carbon battery negative electrode material
Method, it is characterised in that: the staple fiber is one of polypropylene fibre, polyester fiber and acrylic fiber or a variety of, length
For 0.5-2mm.
10. classifying porous lead carbon composite the answering as lead carbon battery negative electrode material of one kind according to claim 7
With method, it is characterised in that: the additive is one of barium sulfate, acetylene black, carbon black and humic acid or a variety of.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113036093A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Modified carbon material and preparation method and application thereof |
| CN113036130A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Carbon material for low-temperature lead-carbon battery and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113036093A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Modified carbon material and preparation method and application thereof |
| CN113036130A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Carbon material for low-temperature lead-carbon battery and preparation method and application thereof |
| CN113036130B (en) * | 2019-12-09 | 2024-03-19 | 中国科学院大连化学物理研究所 | Carbon material for low-temperature lead-carbon battery and preparation method and application thereof |
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Application publication date: 20190301 |