CN103682357A - Graphene composite electrode material and preparation method thereof, lead-carbon battery negative electrode lead plaster and preparation method thereof as well as lead-carbon battery - Google Patents
Graphene composite electrode material and preparation method thereof, lead-carbon battery negative electrode lead plaster and preparation method thereof as well as lead-carbon battery Download PDFInfo
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- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
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Abstract
The invention provides a graphene composite electrode material. The graphene composite electrode material comprises nitrogen-doped graphene and lead sulfate adsorbed between nitrogen-doped graphene sheet layers; the mass ratio of the nitrogen-doped graphene to the lead sulfate is 1:(10-20). When the graphene composite electrode material is applied to a negative electrode of a lead-carbon battery, the nitrogen-doped graphene is a non-polarity material and can be well compatible with electrolyte-sulfuric acid of the lead-carbon battery, so that reduction of the electrochemical polarization of the negative electrode is facilitated. The interlayer spacing of the nitrogen-doped graphene is large so that the specific surface area is large and the nitrogen-doped graphene is suitable for being used as a growing point of a lead sulfate crystalline grain under a large-power condition; the sulfation of the negative electrode under the large-power condition is reduced so that the cycle life of the negative electrode is prolonged and the cycle performance of the lead-carbon battery is improved. The invention further provides a preparation method of the graphene composite electrode material, lead-carbon battery negative electrode lead plaster and a preparation method thereof, and the lead-carbon battery.
Description
Technical field
The present invention relates to battery technology field, particularly relate to a kind of graphene combination electrode material and preparation method, plumbous carbon battery cathode lead plaster and preparation method and plumbous carbon battery.
Background technology
The development of lead-acid battery has had the history of more than 100 year, and it improves the history that product valve-control type lead-acid accumulator (VRLA) has also had decades.Its application is very extensive, mainly comprises at present automobile ignition device, the large-scale energy storage device that small-sized household energy storage device and power plant are used etc.Lead-acid battery is the extensive use of valve-control type lead-acid accumulator especially, mainly gives the credit to that cost is low, the life-span is long, security performance is good, and the recovery utilization rate of old and useless battery up to 95% with first-class feature.Along with deepening continuously of research, lead-acid battery will, towards larger capacity and better high rate performance future development, make it in more field, be used widely.
Due to the development of electric power car, the requirement of battery not only needs to provide long energy supply, more needs battery to work under high magnification, but long heavy-current discharge can make lead-acid battery generation sulfation, thereby affect its useful life.Particularly the negative maximum multiplying power discharging cycle performance of lead-acid battery is poor, and the life-span is short, can not reach the requirement of existing electric power car and energy storage back-up source.
At present, material with carbon element is inserted in plumbous negative pole and become the focus when research to prepare plumbous carbon battery.Material with carbon element can improve the dispersiveness of plumbous active material, improves lead active material utilization, is conducive to improve the cycle performance of plumbous carbon battery.
Yet existing plumbous carbon battery, because negative pole sulfation under high-power condition is serious, causes the cycle life of negative pole shorter, thereby makes the cycle performance of plumbous carbon battery poor, is difficult to meet the requirement of electric power car and energy storage back-up source.
Summary of the invention
Based on this, be necessary to provide graphene combination electrode material of a kind of cycle performance that can improve plumbous carbon battery and preparation method thereof.
Further, provide a kind of plumbous carbon battery cathode lead plaster and preparation method thereof, plumbous carbon battery.
A graphene combination electrode material, comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of described nitrogen-doped graphene sheet interlayer, the mass ratio of described nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
A preparation method for graphene combination electrode material, comprises the steps:
Prepare nitrogen-doped graphene;
In the ratio of 1g:53mL ~ 107mL, described nitrogen-doped graphene be impregnated in the lead acetate solution that concentration is 0.2g/mL, ultrasonic processing 0.5 hour ~ 1 hour, obtains dispersion liquid;
By volume for 100mL:5.4mL ~ 8.1mL is 1.2g/mL sulfuric acid solution to adding concentration in described dispersion liquid, stirring reaction 0.5 hour ~ 1 hour; And
Filter, obtain graphene combination electrode material after dry, described graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of described nitrogen-doped graphene sheet interlayer, and the mass ratio of described nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
In an embodiment, the preparation method of described nitrogen-doped graphene is therein:
Graphite oxide or Graphene are placed in to ammonia atmosphere, with the programming rate of 5 ~ 15 ℃/min, are warming up to 500 ℃ ~ 700 ℃, react 0.5 ~ 1 hour, obtain nitrogen-doped graphene after cooling.
In an embodiment, the preparation method of described nitrogen-doped graphene is therein:
Graphite oxide or Graphene and urea, ammonium carbonate, carbonic hydroammonium, ammonium acetate or melamine are mixed to get to mixture; described mixture programming rate with 5 ~ 15 ℃/min under the condition of inert gas shielding is warming up to 500 ℃ ~ 700 ℃; react 0.5 ~ 1 hour, obtain nitrogen-doped graphene after cooling.
Therein in an embodiment, described dry step is the vacuumize 2 hours ~ 5 hours at 60 ℃ ~ 100 ℃ of filter residue that filtration is obtained.
A plumbous carbon battery cathode lead plaster, comprises the following component by mass parts:
1 ~ 10 part of 100 parts, lead powder, 4 ~ 100 parts, sulfuric acid, 0.1 ~ 8 part of binding agent, 0.1 ~ 2 part, barium sulfate, 0.01 ~ 2 part, liberation of hydrogen inhibitor, 1 ~ 4 part of humic acid, 5 ~ 15 parts of red lead, 12 ~ 21 parts, water, 0.1 ~ 0.2 part, short fiber and graphene combination electrode material;
Wherein, described graphene combination electrode comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of described nitrogen-doped graphene sheet interlayer, and the mass ratio of described nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
In an embodiment, described binding agent is polytetrafluoroethylene, sodium carboxymethylcellulose or butadiene-styrene rubber therein;
Described liberation of hydrogen inhibitor is indium oxide, bismuth oxide, stearic acid, barium stearate, bismuth metal or samarium metal;
Described short fiber is selected from nylon, acrylic fibers or terylene.
In an embodiment, the apparent density of described plumbous carbon battery cathode lead plaster is 3.5g/mL ~ 4.5g/mL therein.
A preparation method for plumbous carbon battery cathode lead plaster, comprises the steps:
By mass parts, 0.1 ~ 0.2 part, 100 parts, lead powder, 0.1 ~ 2 part, barium sulfate, 0.01 ~ 2 part, liberation of hydrogen inhibitor, 1 ~ 10 part of graphene combination electrode material, 1 ~ 4 part of humic acid, 5 ~ 15 parts of red lead, short fiber is mixed to get to mixture, stir 10 minutes ~ 20 minutes;
By mass parts, 12 ~ 21 parts, water is poured in described mixture and obtained slurry, stir 10 minutes ~ 20 minutes;
By mass parts, under agitation, 4 ~ 100 parts, sulfuric acid is added in described slurry, stir 10 minutes ~ 20 minutes; And
By mass parts, in the described slurry that adds sulfuric acid, add 0.1 ~ 8 part of binding agent, stir 5 minutes ~ 20 minutes, obtain plumbous carbon battery cathode lead plaster;
Wherein, described graphene combination electrode comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of described nitrogen-doped graphene sheet interlayer, and the mass ratio of described nitrogen-doped graphene and lead sulfate is 1: 10 ~ 20.
A kind of plumbous carbon battery, comprise battery container and be contained in positive pole, negative pole and the electrolyte in described battery container, described negative pole comprises collector and be coated on the plumbous carbon battery cathode lead plaster on described collector, and described plumbous carbon battery cathode lead plaster comprises the following component by mass parts:
1 ~ 10 part of 100 parts, lead powder, 4 ~ 100 parts, sulfuric acid, 0.1 ~ 8 part of binding agent, 0.1 ~ 2 part, barium sulfate, 0.01 ~ 2 part, liberation of hydrogen inhibitor, 1 ~ 4 part of humic acid, 5 ~ 15 parts of red lead, 12 ~ 21 parts, water, 0.1 ~ 0.2 part, short fiber and graphene combination electrode material; Wherein, described graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of described nitrogen-doped graphene sheet interlayer, and the mass ratio of described nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
Above-mentioned graphene combination electrode material is adsorbed in nitrogen-doped graphene sheet interlayer by lead sulfate and forms, when this graphene combination electrode material is applied to the negative pole of plumbous carbon battery, because nitrogen-doped graphene is non-polar material, there is good compatibility with the electrolyte-sulfuric acid of plumbous carbon battery, be conducive to reduce the electrochemical polarization of negative pole.And the interlamellar spacing of nitrogen-doped graphene is larger, thereby there is higher specific area, under high-power condition, be suitable as the growing point of lead sulfate crystal grain, reduce negative pole sulfation under high-power condition, thereby improved the cycle life of negative pole, improved the cycle performance of plumbous carbon battery.
Accompanying drawing explanation
Fig. 1 is preparation method's flow chart of the graphene combination electrode material of an execution mode;
Fig. 2 is preparation method's flow chart of the plumbous carbon battery cathode lead plaster of an execution mode;
Fig. 3 for use embodiment 1 graphene combination electrode material plumbous carbon battery at 25 ℃, 5mA/cm
2under cycle performance figure.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public concrete enforcement.
The graphene combination electrode material of one execution mode, comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer.The mass ratio of nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
Lead sulfate chemisorbed is in nitrogen-doped graphene sheet interlayer.
During plumbous carbon battery electric discharge, there is reaction as follows:
PbO
2+Pb+2H
2SO
4→2PbSO
4+2H
2O
By this graphene combination electrode material, for plumbous carbon battery, in use, in graphene combination electrode material, the effect of lead sulfate is exactly to be lead sulfate (PbSO when plumbous carbon battery electric discharge to plumbous carbon battery
4) deposition provides a large amount of nucleus.Provide very large surface allow PbSO
4deposition, will make so short grained lead sulfate generate in a large number, and hard, thick lead sulfate has obtained inhibition.And granule lead sulfate solubility is high, can when battery charges, be reduced to biscuit lead, thereby have improved the cycle life of battery.
Because nitrogen-doped graphene has the conductivity of superelevation, than high 1 ~ 2 order of magnitude of general material with carbon element (as Graphene, activated carbon etc.).Therefore the graphene combination electrode material that nitrogen-doped graphene is adsorbed to lead sulfate formation is for plumbous carbon battery, and plumbous carbon battery is when high current charge-discharge, and its capacitive property has better conservation rate.
And due to the high conductivity of nitrogen-doped graphene, when introducing the negative pole of lead carbon battery, the material with carbon element that the amount of needs is relatively general is greatly less, there is no limit and adds conductive agent outward, has been conducive to reduce the cost of lead carbon battery.
General material with carbon element is nonpolar, the compatibility of the polarity electrolyte-sulfuric acid in nonpolar material with carbon element and plumbous carbon battery is bad, and nitrogen-doped graphene is polarity, is conducive to strengthen the compatibility of graphene combination electrode material and electrolyte, thereby is conducive to reduce the electrochemical polarization of negative pole.
The interlamellar spacing of nitrogen-doped graphene is larger than Graphene, and with respect to Graphene, its specific area increases by 30 ~ 50%, is more suitable for the growing point as lead sulfate crystal grain under high-power condition, has reduced negative pole sulfation under high-power condition, has improved cycle life.
This graphene combination electrode material has larger specific area, also increased the double layer capacity of this material, while being applied to plumbous carbon battery, this graphene combination electrode material can be shared part electric current when large multiplying power discharging, be conducive to extend the life-span of negative pole, improve the cycle life of negative pole.
The effect of lead sulfate is to provide nucleus, and the Main Function of nitrogen-doped graphene is conduction.The amount of nitrogen-doped graphene has just reduced the ratio of active material in electrode too much, has reduced the energy density of battery; The amount of nitrogen-doped graphene can not form effective conductive network in electrode interior very little, cannot improve conductivity.
The mass ratio of nitrogen-doped graphene and lead sulfate is for being preferably 1:15 ~ 20.Nitrogen-doped graphene and lead sulfate be take graphene combination electrode material that mass ratio forms as 1:15 ~ 20 and can be made full use of the characteristic of nitrogen-doped graphene high conductivity, high-specific surface area, and can provide again enough lead sulfates to take when plumbous carbon battery electric discharge is lead sulfate (PbSO
4) deposition nucleus is provided so that apply the better performances of the plumbous carbon battery of this graphene combination electrode material.
And, it is graphene combination electrode material that 1:15 ~ 20 form while being applied to the electrode of plumbous carbon battery that nitrogen-doped graphene and lead sulfate be take to mass ratio, and the amount of nitrogen-doped graphene is unlikely to too much and reduces the ratio of active material in electrode and reduced the energy density of battery.
When this graphene combination electrode material is applied to the negative pole of plumbous carbon battery, because nitrogen-doped graphene is non-polar material, there is good intermiscibility with the electrolyte of plumbous carbon battery, be conducive to reduce the electrochemical polarization of negative pole.And the interlamellar spacing of nitrogen-doped graphene is larger, thereby there is higher specific area, under high-power condition, be suitable as the growing point of lead sulfate crystal grain, reduce negative pole sulfation under high-power condition, thereby improved the cycle life of negative pole, improved the cycle performance of plumbous carbon battery.
Refer to Fig. 1, the preparation method of the graphene combination electrode material of an execution mode, comprises the steps:
Step S110: prepare nitrogen-doped graphene.
Graphite oxide or Graphene are placed in to ammonia atmosphere, with the programming rate of 5 ~ 15 ℃/min, are warming up to 500 ℃ ~ 700 ℃, react 0.5 ~ 1 hour, obtain nitrogen-doped graphene after cooling.
Graphite oxide or Graphene can be positioned in muffle furnace, and pass into ammonia in muffle furnace, then be warming up to reaction at 500 ℃ ~ 700 ℃.The flow velocity of ammonia is preferably 400mL/min, to guarantee that graphite oxide or Graphene fully contact with ammonia.
In other embodiments, also can be by graphite oxide or Graphene and urea (CN
2h
4o), ammonium carbonate ((NH
4)
2cO
3), carbonic hydroammonium (NH
4hCO
3), ammonium acetate (CH
3cOONH
4) and melamine (C
3h
6n
6) in a kind of mixture that is mixed to get, mixture programming rate with 5 ~ 15 ℃/min under the condition of inert gas shielding is warming up to 500 ℃ ~ 700 ℃, react 0.5 ~ 1 hour, obtain nitrogen-doped graphene after cooling.
Graphite oxide or Graphene and urea (CN
2h
4o), ammonium carbonate ((NH
4)
2cO
3), carbonic hydroammonium (NH
4hCO
3), ammonium acetate (CH
3cOONH
4) and melamine (C
3h
6n
6) in a kind of mass ratio be 1:1 ~ 10.
Above-mentioned two kinds the method technique of preparing nitrogen-doped graphene is simple, easy to operate, controllability is good.
Step S120: in the ratio of 1g:53mL ~ 107mL, nitrogen-doped graphene be impregnated in the lead acetate solution that concentration is 0.2g/mL, ultrasonic processing 0.5 hour ~ 1 hour, obtains dispersion liquid.
Nitrogen-doped graphene impregnated in lead acetate solution, carries out ultrasonic processing, makes lead acetate be adsorbed in the sheet interlayer of nitrogen-doped graphene.
Preferably, the power of ultrasonic processing is 600 ~ 800w, to shorten the time of ultrasonic processing, and avoids the destruction to nitrogen-doped graphene, keeps the high conductivity of nitrogen-doped graphene.
Step S130: by volume for 100mL:5.4mL ~ 8.1mL is 1.2g/mL sulfuric acid solution to adding concentration in dispersion liquid, stirring reaction 0.5 hour ~ 1 hour.
Sulfuric acid and lead acetate react, and generate lead sulfate precipitation.Lead sulfate chemisorbed is in nitrogen-doped graphene sheet interlayer.
Step S140: obtain graphene combination electrode material after filtering, being dried.
By after the reacting liquid filtering of step S130, filter residue vacuumize at 60 ℃ ~ 100 ℃ is obtained to graphene combination electrode material for 2 hours ~ 5 hours.
This graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer.The mass ratio of nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
The preparation method of above-mentioned graphene combination electrode material is first adsorbed in lead acetate nitrogen-doped graphene sheet interlayer, and then by sulfuric acid, reacts with lead acetate and generate the lead sulfate be adsorbed in nitrogen-doped graphene sheet interlayer and precipitate.Lead acetate is water-soluble, and nitrogen-doped graphene be impregnated in lead acetate solution and ultrasonic processing, is easy to make lead acetate to be adsorbed in nitrogen-doped graphene sheet interlayer.
Preparation method's technique of above-mentioned graphene combination electrode material is simple, low for equipment requirements, is conducive to large-scale production.
The plumbous carbon battery cathode lead plaster of one execution mode, comprises the following component by mass parts:
1 ~ 10 part of 100 parts, lead powder, 4 ~ 100 parts, sulfuric acid, 0.1 ~ 8 part of binding agent, 0.1 ~ 2 part, barium sulfate, 0.01 ~ 2 part, liberation of hydrogen inhibitor, 1 ~ 4 part of humic acid, 5 ~ 15 parts of red lead, 12 ~ 21 parts, water, 0.1 ~ 0.2 part, short fiber and graphene combination electrode material.
Wherein, binding agent is polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC) or butadiene-styrene rubber (SBR).
Liberation of hydrogen inhibitor is indium oxide (In
2o
3), bismuth oxide (Bi
2o
3), stearic acid (C
18h
36o
2), barium stearate (C
36h
70baO
4), bismuth metal (Bi) or samarium metal (Sm).
Short fiber is nylon (PA), acrylic fibers or terylene.Short fiber, for increasing plumbous carbon battery cathode lead plaster, prevents from coming off from collector.
Sulfuric acid is that concentration is the sulfuric acid of 1.1 ~ 1.4g/mL.
Graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer.The mass ratio of nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
The apparent density of this lead carbon battery cathode lead plaster is 3.5g/mL ~ 4.5g/mL.Apparent density is that the plumbous carbon battery cathode lead plaster of 3.5g/mL ~ 4.5g/mL has suitable viscosity, is conducive to it to be coated on equably and on collector, to obtain high-quality negative pole.
Brown lead oxide (PbO just very
2) plate.
In above-mentioned lead carbon battery cathode lead plaster, contain graphene combination electrode material, graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer.The mass ratio of nitrogen-doped graphene and lead sulfate is 1: 10 ~ 20.This graphene combination electrode material can reduce negative pole sulphation and electrochemical polarization under high-power condition, while making this lead carbon battery cathode lead plaster be applied to plumbous carbon battery, can improve the cycle performance of plumbous carbon battery.
Refer to Fig. 2, the preparation method of the plumbous carbon battery cathode lead plaster of an execution mode, comprises the steps:
Step S210: by mass parts, 0.1 ~ 0.2 part, 100 parts, lead powder, 0.1 ~ 2 part, barium sulfate, 0.01 ~ 2 part, liberation of hydrogen inhibitor, 1 ~ 10 part of graphene combination electrode material, 1 ~ 4 part of humic acid, 5 ~ 15 parts of red lead, short fiber is mixed to get to mixture, stirs 10 minutes ~ 20 minutes.
Stir 10 minutes ~ 20 minutes, so that each component mixes.
Liberation of hydrogen inhibitor is indium oxide, bismuth oxide, stearic acid, barium stearate, bismuth metal or samarium metal.
Short fiber is nylon, acrylic fibers or terylene.
Graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer.The mass ratio of nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
Step S220: by mass parts, 12 ~ 21 parts, water is poured in mixture and obtained slurry, stir 10 minutes ~ 20 minutes.
The process that adds water completed in 1 minute.Fully stir, further make each component be mixed to get more even, obtain slurry.
Step S230: by mass parts, under agitation, 4 ~ 100 parts, sulfuric acid is added in slurry, stir 10 minutes ~ 20 minutes.
Sulfuric acid is that concentration is the sulfuric acid of 1.1 ~ 1.4g/mL.
The whole process that adds sulfuric acid is 10 minutes ~ 20 minutes, and the process that adds sulfuric acid keeps constantly stirring, and controls temperature simultaneously and is no more than 70 ℃.
Step S240: by mass parts, add 0.1 ~ 8 part of binding agent to having added in the slurry of sulfuric acid, stir 5 minutes ~ 20 minutes, obtain plumbous carbon battery cathode lead plaster.
Binding agent is polytetrafluoroethylene, sodium carboxymethylcellulose or butadiene-styrene rubber.
The apparent density that obtains plumbous carbon battery cathode lead plaster is 3.5g/mL ~ 4.5g/mL.
The preparation method of above-mentioned plumbous carbon battery cathode lead plaster, by repeatedly feeding intake and repeatedly stirring, mixes lead plaster comparatively uniformly to obtain each component.
This preparation method's technique is simple, carries out at normal temperatures, and mild condition, low for equipment requirements, preparation cost is low.
The plumbous carbon battery of one execution mode, comprises battery container and is contained in positive pole, negative pole and the electrolyte in described battery container.
Negative pole comprises collector and is coated on the plumbous carbon battery cathode lead plaster on collector.Plumbous carbon battery cathode lead plaster comprises the following component by mass parts:
1 ~ 10 part of 100 parts, lead powder, 4 ~ 100 parts, sulfuric acid, 0.1 ~ 8 part of binding agent, 0.1 ~ 2 part, barium sulfate, 0.01 ~ 2 part, liberation of hydrogen inhibitor, 1 ~ 4 part of humic acid, 5 ~ 15 parts of red lead, 12 ~ 21 parts, water, 0.1 ~ 0.2 part, short fiber and graphene combination electrode material.
Wherein, binding agent is polytetrafluoroethylene, sodium carboxymethylcellulose or butadiene-styrene rubber.
Liberation of hydrogen inhibitor is indium oxide, bismuth oxide, stearic acid, barium stearate, bismuth metal or samarium metal.
Short fiber is selected from nylon, acrylic fibers or terylene.
Sulfuric acid is that concentration is the sulfuric acid of 1.1 ~ 1.4g/mL.
Graphene combination electrode comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer.The mass ratio of nitrogen-doped graphene and lead sulfate is 1: 10 ~ 20.
Lead sulfate-nitrogen-doped graphene can reduce negative electricity polarization and in high-power lower sulphation, be conducive to improve the cycle life of negative pole, thereby improved the cycle performance of this lead carbon battery.
It is below specific embodiment.
Embodiment 1
(1) prepare nitrogen-doped graphene
Graphene is put into the muffle furnace of protection of ammonia, the flow velocity of ammonia is 400mL/min, with the programming rate of 5 ℃/min, is warming up to 500 ℃, reacts 1 hour, obtains nitrogen-doped graphene after cooling.
(2) prepare graphene combination electrode material
In the ratio of 1g:107mL, nitrogen-doped graphene be impregnated in the lead acetate solution that concentration is 0.2g/mL, ultrasonic processing 0.5 hour, obtains dispersion liquid; By volume for 100mL:5.4mL is 1.2g/mL sulfuric acid solution to adding concentration in dispersion liquid, stirring reaction obtains reactant liquor for 0.5 hour, by reacting liquid filtering, filter residue vacuumize at 60 ℃ is obtained to graphene combination electrode material for 5 hours, this graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer, and the mass ratio of nitrogen-doped graphene and lead sulfate is 1:20.
(3) prepare plumbous carbon battery cathode lead plaster
According to mass parts, take respectively: 1 part of 100 parts, lead powder, 0.1 part, barium sulfate, 0.01 part, liberation of hydrogen inhibitor, 1 part of humic acid, 5 parts of red lead, 0.1 part, short fiber and above-mentioned graphene combination electrode material, above-mentioned each component is poured into and in container, obtained mixture, stir 10 minutes, each component of this mixture is mixed fully.Wherein, liberation of hydrogen inhibitor is indium oxide, and short fiber is nylon;
By mass parts, 12 parts, water is added fast in said mixture and obtains slurry, the whole process that adds water completed in 1 minute, then stirred 10 minutes;
By mass parts, under agitation, 4 parts, the sulfuric acid that is 1.1g/mL by concentration joins in above-mentioned slurry slowly, and the whole process that adds sulfuric acid is 10 minutes, controls temperature and be no more than 70 ℃ in adding the process of sulfuric acid, adds rear continuation and stirs 10 minutes;
By mass parts, in the above-mentioned slurry that adds sulfuric acid, add 0.1 part of binding agent, stir 5 minutes, obtain plumbous carbon battery cathode lead plaster.Wherein, binding agent is polytetrafluoroethylene.
(4) prepare plumbous carbon battery
Above-mentioned plumbous carbon battery cathode lead plaster is coated on plumbous collector and obtains negative pole.Positive pole and negative pole are contained in battery container and inject sulfuric acid as electrolyte, and sealed cell housing obtains plumbous carbon battery.
Test this lead carbon battery at 25 ℃, 5mA/cm
2under cycle performance.Test result as shown in Figure 3.As seen from Figure 3, this lead carbon battery is with 5mA/cm
2large multiplying power condition under after 6000 circulations, its Capacitance reserve, more than 90%, has good cycle performance.
Embodiment 2
(1) prepare nitrogen-doped graphene
1:1 puts into muffle furnace after Graphene is mixed with urea in mass ratio, with the programming rate of 15 ℃/min, is warming up to 700 ℃, reacts 0.5 hour, obtains nitrogen-doped graphene after cooling.
(2) prepare graphene combination electrode material
In the ratio of 1g:53mL, nitrogen-doped graphene be impregnated in the lead acetate solution that concentration is 0.2g/mL, ultrasonic processing 1 hour, obtains dispersion liquid; By volume for 100mL:8.1mL is 1.2g/mL sulfuric acid solution to adding concentration in dispersion liquid, stirring reaction obtains reactant liquor for 1 hour, by reacting liquid filtering, filter residue vacuumize at 100 ℃ is obtained to graphene combination electrode material for 2 hours, this graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer, and the mass ratio of nitrogen-doped graphene and lead sulfate is 1:10.
(3) prepare plumbous carbon battery cathode lead plaster
According to mass parts, take respectively: 2 parts of 100 parts, lead powder, 0.3 part, barium sulfate, 0.1 part, liberation of hydrogen inhibitor, 1.5 parts of humic acids, 6 parts of red lead, 0.12 part, short fiber and above-mentioned graphene combination electrode materials, above-mentioned each component is poured into and in container, obtained mixture, stir 20 minutes, each component of this mixture is mixed fully.Wherein, liberation of hydrogen inhibitor is bismuth oxide, and short fiber is acrylic fibers;
By mass parts, 13 parts, water is added fast in said mixture and obtains slurry, the whole process that adds water completed in 1 minute, then stirred 20 minutes;
By mass parts, under agitation, 10 parts, the sulfuric acid that is 1.1g/mL by concentration joins in above-mentioned slurry slowly, and the whole process that adds sulfuric acid is 10 minutes, controls temperature and be no more than 70 ℃ in adding the process of sulfuric acid, adds rear continuation and stirs 20 minutes;
By mass parts, in the above-mentioned slurry that adds sulfuric acid, add 1 part of binding agent, stir 10 minutes, obtain plumbous carbon battery cathode lead plaster.Wherein, binding agent is sodium carboxymethylcellulose.
(4) prepare plumbous carbon battery
Above-mentioned plumbous carbon battery cathode lead plaster is coated on plumbous collector and obtains negative pole.Positive pole and negative pole are contained in battery container and inject electrolyte, and sealed cell housing obtains plumbous carbon battery.
Embodiment 3
(1) prepare nitrogen-doped graphene
1:10 puts into muffle furnace after Graphene is mixed with ammonium carbonate in mass ratio, with the programming rate of 5 ℃/min, is warming up to 600 ℃, reacts 1 hour, obtains nitrogen-doped graphene after cooling.
(2) prepare graphene combination electrode material
In the ratio of 1g:79.5mL, nitrogen-doped graphene be impregnated in the lead acetate solution that concentration is 0.2g/mL, ultrasonic processing 0.8 hour, obtains dispersion liquid; By volume for 100mL:6.0mL is 1.2g/mL sulfuric acid solution to adding concentration in dispersion liquid, stirring reaction obtains reactant liquor for 0.8 hour, by reacting liquid filtering, filter residue vacuumize at 80 ℃ is obtained to graphene combination electrode material for 3 hours, this graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer, and the mass ratio of nitrogen-doped graphene and lead sulfate is 1:15.
(3) prepare plumbous carbon battery cathode lead plaster
According to mass parts, take respectively: 3 parts of 100 parts, lead powder, 0.6 part, barium sulfate, 0.5 part, liberation of hydrogen inhibitor, 1.9 parts of humic acids, 7 parts of red lead, 0.13 part, short fiber and above-mentioned graphene combination electrode materials, above-mentioned each component is poured into and in container, obtained mixture, stir 15 minutes, each component of this mixture is mixed fully.Wherein, liberation of hydrogen inhibitor is stearic acid, and short fiber is terylene;
By mass parts, 14 parts, water is added fast in said mixture and obtains slurry, the whole process that adds water completed in 1 minute, then stirred 15 minutes;
By mass parts, under agitation, 20 parts, the sulfuric acid that is 1.2g/mL by concentration joins in above-mentioned slurry slowly, and the whole process that adds sulfuric acid is 10 minutes, controls temperature and be no more than 70 ℃ in adding the process of sulfuric acid, adds rear continuation and stirs 15 minutes;
By mass parts, in the above-mentioned slurry that adds sulfuric acid, add 2 parts of binding agents, stir 15 minutes, obtain plumbous carbon battery cathode lead plaster.Wherein, binding agent is butadiene-styrene rubber.
(4) prepare plumbous carbon battery
Above-mentioned plumbous carbon battery cathode lead plaster is coated on plumbous collector and obtains negative pole.Positive pole and negative pole are contained in battery container and inject electrolyte, and sealed cell housing obtains plumbous carbon battery.
Embodiment 4
(1) prepare nitrogen-doped graphene
1:2 puts into muffle furnace after Graphene is mixed with carbonic hydroammonium in mass ratio, with the programming rate of 5 ℃/min, is warming up to 650 ℃, reacts 1 hour, obtains nitrogen-doped graphene after cooling.
(2) prepare graphene combination electrode material
In the ratio of 1g:63.6mL, nitrogen-doped graphene be impregnated in the lead acetate solution that concentration is 0.2g/mL, ultrasonic processing 0.8 hour, obtains dispersion liquid; By volume for 100mL:6.4mL is 1.2g/mL sulfuric acid solution to adding concentration in dispersion liquid, stirring reaction obtains reactant liquor for 1 hour, by reacting liquid filtering, filter residue vacuumize at 70 ℃ is obtained to graphene combination electrode material for 4 hours, this graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer, and the mass ratio of nitrogen-doped graphene and lead sulfate is 1:12.
(3) prepare plumbous carbon battery cathode lead plaster
According to mass parts, take respectively: 5 parts of 100 parts, lead powder, 1 part, barium sulfate, 0.8 part, liberation of hydrogen inhibitor, 1.4 parts of humic acids, 8 parts of red lead, 0.14 part, short fiber and above-mentioned graphene combination electrode materials, above-mentioned each component is poured into and in container, obtained mixture, stir 15 minutes, each component of this mixture is mixed fully.Wherein, liberation of hydrogen inhibitor is barium stearate, and short fiber is nylon;
By mass parts, 15 parts, water is added fast in said mixture and obtains slurry, the whole process that adds water completed in 1 minute, then stirred 15 minutes;
By mass parts, under agitation, 50 parts, the sulfuric acid that is 1.2g/mL by concentration joins in above-mentioned slurry slowly, and the whole process that adds sulfuric acid is 10 minutes, controls temperature and be no more than 70 ℃ in adding the process of sulfuric acid, adds rear continuation and stirs 15 minutes;
By mass parts, in the above-mentioned slurry that adds sulfuric acid, add 3 parts of binding agents, stir 20 minutes, obtain plumbous carbon battery cathode lead plaster.Wherein, binding agent is polytetrafluoroethylene.
(4) prepare plumbous carbon battery
Above-mentioned plumbous carbon battery cathode lead plaster is coated on plumbous collector and obtains negative pole.Positive pole and negative pole are contained in battery container and inject electrolyte, and sealed cell housing obtains plumbous carbon battery.
Embodiment 5
(1) prepare nitrogen-doped graphene
1:5 puts into muffle furnace after Graphene is mixed with ammonium acetate in mass ratio, with the programming rate of 8 ℃/min, is warming up to 500 ℃, reacts 0.9 hour, obtains nitrogen-doped graphene after cooling.
(2) prepare graphene combination electrode material
In the ratio of 1g:74.2mL, nitrogen-doped graphene be impregnated in the lead acetate solution that concentration is 0.2g/mL, ultrasonic processing 0.5 hour, obtains dispersion liquid; By volume for 100mL:6.8mL is 1.2g/mL sulfuric acid solution to adding concentration in dispersion liquid, stirring reaction obtains reactant liquor for 0.5 hour, by reacting liquid filtering, filter residue vacuumize at 70 ℃ is obtained to graphene combination electrode material for 4 hours, this graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer, and the mass ratio of nitrogen-doped graphene and lead sulfate is 1:14.
(3) prepare plumbous carbon battery cathode lead plaster
According to mass parts, take respectively: 6 parts of 100 parts, lead powder, 1.3 parts, barium sulfate, 1 part, liberation of hydrogen inhibitor, 2.5 parts of humic acids, 9 parts of red lead, 0.15 part, short fiber and above-mentioned graphene combination electrode materials, above-mentioned each component is poured into and in container, obtained mixture, stir 18 minutes, each component of this mixture is mixed fully.Wherein, liberation of hydrogen inhibitor is bismuth metal, and short fiber is acrylic fibers;
By mass parts, 16 parts, water is added fast in said mixture and obtains slurry, the whole process that adds water completed in 1 minute, then stirred 18 minutes;
By mass parts, under agitation, 60 parts, the sulfuric acid that is 1.3g/mL by concentration joins in above-mentioned slurry slowly, and the whole process that adds sulfuric acid is 10 minutes, controls temperature and be no more than 70 ℃ in adding the process of sulfuric acid, adds rear continuation and stirs 18 minutes;
By mass parts, in the above-mentioned slurry that adds sulfuric acid, add 4 parts of binding agents, stir 15 minutes, obtain plumbous carbon battery cathode lead plaster.Wherein, binding agent is sodium carboxymethylcellulose.
(4) prepare plumbous carbon battery
Above-mentioned plumbous carbon battery cathode lead plaster is coated on plumbous collector and obtains negative pole.Positive pole and negative pole are contained in battery container and inject electrolyte, and sealed cell housing obtains plumbous carbon battery.
Embodiment 6
(1) prepare nitrogen-doped graphene
1:7 puts into muffle furnace after Graphene is mixed with melamine in mass ratio, with the programming rate of 15 ℃/min, is warming up to 700 ℃, reacts 0.8 hour, obtains nitrogen-doped graphene after cooling.
(2) prepare graphene combination electrode material
In the ratio of 1g:68.9mL, nitrogen-doped graphene be impregnated in the lead acetate solution that concentration is 0.2g/mL, ultrasonic processing 0.6 hour, obtains dispersion liquid; By volume for 100mL:7.2mL is 1.2g/mL sulfuric acid solution to adding concentration in dispersion liquid, stirring reaction obtains reactant liquor for 0.6 hour, by reacting liquid filtering, filter residue vacuumize at 90 ℃ is obtained to graphene combination electrode material for 3 hours, this graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer, and the mass ratio of nitrogen-doped graphene and lead sulfate is 1:13.
(3) prepare plumbous carbon battery cathode lead plaster
According to mass parts, take respectively: 7 parts of 100 parts, lead powder, 1.6 parts, barium sulfate, 1.3 parts, liberation of hydrogen inhibitor, 3 parts of humic acids, 12 parts of red lead, 0.17 part, short fiber and above-mentioned graphene combination electrode materials, above-mentioned each component is poured into and in container, obtained mixture, stir 16 minutes, each component of this mixture is mixed fully.Wherein, liberation of hydrogen inhibitor is samarium metal, and short fiber is terylene;
By mass parts, 17 parts, water is added fast in said mixture and obtains slurry, the whole process that adds water completed in 1 minute, then stirred 16 minutes;
By mass parts, under agitation, 70 parts, the sulfuric acid that is 1.3g/mL by concentration joins in above-mentioned slurry slowly, and the whole process that adds sulfuric acid is 10 minutes, controls temperature and be no more than 70 ℃ in adding the process of sulfuric acid, adds rear continuation and stirs 16 minutes;
By mass parts, in the above-mentioned slurry that adds sulfuric acid, add 5 parts of binding agents, stir 18 minutes, obtain plumbous carbon battery cathode lead plaster.Wherein, binding agent is butadiene-styrene rubber.
(4) prepare plumbous carbon battery
Above-mentioned plumbous carbon battery cathode lead plaster is coated on plumbous collector and obtains negative pole.Positive pole and negative pole are contained in battery container and inject electrolyte, and sealed cell housing obtains plumbous carbon battery.
Embodiment 7
(1) prepare nitrogen-doped graphene
1:9 puts into muffle furnace after Graphene is mixed with melamine in mass ratio, with the programming rate of 10 ℃/min, is warming up to 550 ℃, reacts 0.7 hour, obtains nitrogen-doped graphene after cooling.
(2) prepare graphene combination electrode material
In the ratio of 1g:79.5mL, nitrogen-doped graphene be impregnated in the lead acetate solution that concentration is 0.2g/mL, ultrasonic processing 1 hour, obtains dispersion liquid; By volume for 100mL:7.5mL is 1.2g/mL sulfuric acid solution to adding concentration in dispersion liquid, stirring reaction obtains reactant liquor for 1 hour, by reacting liquid filtering, filter residue vacuumize at 60 ℃ is obtained to graphene combination electrode material for 5 hours, this graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer, and the mass ratio of nitrogen-doped graphene and lead sulfate is 1:15.
(3) prepare plumbous carbon battery cathode lead plaster
According to mass parts, take respectively: 8 parts of 100 parts, lead powder, 1.8 parts, barium sulfate, 1.6 parts, liberation of hydrogen inhibitor, 3.5 parts of humic acids, 14 parts of red lead, 0.19 part, short fiber and above-mentioned graphene combination electrode materials, above-mentioned each component is poured into and in container, obtained mixture, stir 15 minutes, each component of this mixture is mixed fully.Wherein, liberation of hydrogen inhibitor is bismuth oxide, and short fiber is terylene;
By mass parts, 19 parts, water is added fast in said mixture and obtains slurry, the whole process that adds water completed in 1 minute, then stirred 15 minutes;
By mass parts, under agitation, 80 parts, the sulfuric acid that is 1.4g/mL by concentration joins in above-mentioned slurry slowly, and the whole process that adds sulfuric acid is 10 minutes, controls temperature and be no more than 70 ℃ in adding the process of sulfuric acid, adds rear continuation and stirs 15 minutes;
By mass parts, in the above-mentioned slurry that adds sulfuric acid, add 6 parts of binding agents, stir 20 minutes, obtain plumbous carbon battery cathode lead plaster.Wherein, binding agent is polytetrafluoroethylene.
(4) prepare plumbous carbon battery
Above-mentioned plumbous carbon battery cathode lead plaster is coated on plumbous collector and obtains negative pole.Positive pole and negative pole are contained in battery container and inject electrolyte, and sealed cell housing obtains plumbous carbon battery.
Embodiment 8
(1) prepare nitrogen-doped graphene
1:10 puts into muffle furnace after Graphene is mixed with ammonium carbonate in mass ratio, with the programming rate of 5 ℃/min, is warming up to 700 ℃, reacts 0.5 hour, obtains nitrogen-doped graphene after cooling.
(2) prepare graphene combination electrode material
In the ratio of 1g:107mL, nitrogen-doped graphene be impregnated in the lead acetate solution that concentration is 0.2g/mL, ultrasonic processing 1 hour, obtains dispersion liquid; By volume for 100mL:7.9mL is 1.2g/mL sulfuric acid solution to adding concentration in dispersion liquid, stirring reaction obtains reactant liquor for 1 hour, by reacting liquid filtering, filter residue vacuumize at 100 ℃ is obtained to graphene combination electrode material for 2 hours, this graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of nitrogen-doped graphene sheet interlayer, and the mass ratio of nitrogen-doped graphene and lead sulfate is 1:20.
(3) prepare plumbous carbon battery cathode lead plaster
According to mass parts, take respectively: 10 parts of 100 parts, lead powder, 2 parts, barium sulfate, 2 parts, liberation of hydrogen inhibitor, 4 parts of humic acids, 15 parts of red lead, 0.2 part, short fiber and above-mentioned graphene combination electrode materials, above-mentioned each component is poured into and in container, obtained mixture, stir 12 minutes, each component of this mixture is mixed fully.Wherein, liberation of hydrogen inhibitor is indium oxide, and short fiber is acrylic fibers;
By mass parts, 21 parts, water is added fast in said mixture and obtains slurry, the whole process that adds water completed in 1 minute, then stirred 12 minutes;
By mass parts, under agitation, 100 parts, the sulfuric acid that is 1.4g/mL by concentration joins in above-mentioned slurry slowly, and the whole process that adds sulfuric acid is 10 minutes, controls temperature and be no more than 70 ℃ in adding the process of sulfuric acid, adds rear continuation and stirs 12 minutes;
By mass parts, in the above-mentioned slurry that adds sulfuric acid, add 8 parts of binding agents, stir 12 minutes, obtain plumbous carbon battery cathode lead plaster.Wherein, binding agent is sodium carboxymethylcellulose.
(4) prepare plumbous carbon battery
Above-mentioned plumbous carbon battery cathode lead plaster is coated on plumbous collector and obtains negative pole.Positive pole and negative pole are contained in battery container and inject electrolyte, and sealed cell housing obtains plumbous carbon battery.
The design parameter of plumbous each component of carbon battery cathode lead plaster of embodiment 1 ~ 8 is as shown in following table 1 ~ table 3.
The mass fraction of each component of the plumbous carbon battery cathode lead plaster of table 1 embodiment 1 ~ 8
The kind of liberation of hydrogen inhibitor, binding agent and the short fiber of the plumbous carbon battery cathode lead plaster of table 2 embodiment 1 ~ 8
| Liberation of hydrogen inhibitor | Binding agent | Short fiber |
| Embodiment 1 | Polytetrafluoroethylene | Indium oxide | Nylon |
| Embodiment 2 | Sodium carboxymethylcellulose | Bismuth oxide | Acrylic fibers |
| Embodiment 3 | Butadiene-styrene rubber | Stearic acid | Terylene |
| Embodiment 4 | Polytetrafluoroethylene | Barium stearate | Nylon |
| Embodiment 5 | Sodium carboxymethylcellulose | Bismuth metal | Acrylic fibers |
| Embodiment 6 | Butadiene-styrene rubber | Samarium metal | Terylene |
| Embodiment 7 | Polytetrafluoroethylene | Bismuth oxide | Terylene |
| Embodiment 8 | Sodium carboxymethylcellulose | Indium oxide | Acrylic fibers |
The mass ratio of nitrogen-doped graphene and lead sulfate in the concentration of the sulfuric acid of the plumbous carbon battery cathode lead plaster of table 3 embodiment 1 ~ 8 and graphene combination electrode material
| Concentration (the g/cm of sulfuric acid 3） | The mass ratio of nitrogen-doped graphene and lead sulfate | |
| Embodiment 1 | 1.1 | 1:20 |
| Embodiment 2 | 1.1 | 1:10 |
| Embodiment 3 | 1.2 | 1:15 |
| Embodiment 4 | 1.2 | 1:12 |
| Embodiment 5 | 1.3 | 1:14 |
| Embodiment 6 | 1.3 | 1:13 |
| Embodiment 7 | 1.4 | 1:15 |
| Embodiment 8 | 1.4 | 1:20 |
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a graphene combination electrode material, is characterized in that, comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of described nitrogen-doped graphene sheet interlayer, and the mass ratio of described nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
2. a preparation method for graphene combination electrode material, is characterized in that, comprises the steps:
Prepare nitrogen-doped graphene;
In the ratio of 1g:53mL ~ 107mL, described nitrogen-doped graphene be impregnated in the lead acetate solution that concentration is 0.2g/mL, ultrasonic processing 0.5 hour ~ 1 hour, obtains dispersion liquid;
By volume for 100mL:5.4mL ~ 8.1mL is 1.2g/mL sulfuric acid solution to adding concentration in described dispersion liquid, stirring reaction 0.5 hour ~ 1 hour; And
Filter, obtain graphene combination electrode material after dry, described graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of described nitrogen-doped graphene sheet interlayer, and the mass ratio of described nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
3. the preparation method of graphene combination electrode material according to claim 2, is characterized in that, the preparation method of described nitrogen-doped graphene is:
Graphite oxide or Graphene are placed in to ammonia atmosphere, with the programming rate of 5 ~ 15 ℃/min, are warming up to 500 ℃ ~ 700 ℃, react 0.5 ~ 1 hour, obtain nitrogen-doped graphene after cooling.
4. the preparation method of graphene combination electrode material according to claim 2, is characterized in that, the preparation method of described nitrogen-doped graphene is:
Graphite oxide or Graphene and urea, ammonium carbonate, carbonic hydroammonium, ammonium acetate or melamine are mixed to get to mixture; described mixture programming rate with 5 ~ 15 ℃/min under the condition of inert gas shielding is warming up to 500 ℃ ~ 700 ℃; react 0.5 ~ 1 hour, obtain nitrogen-doped graphene after cooling.
5. the preparation method of graphene combination electrode material according to claim 2, is characterized in that, described dry step is the vacuumize 2 hours ~ 5 hours at 60 ℃ ~ 100 ℃ of filter residue that filtration is obtained.
6. a plumbous carbon battery cathode lead plaster, is characterized in that, comprises the following component by mass parts:
1 ~ 10 part of 100 parts, lead powder, 4 ~ 100 parts, sulfuric acid, 0.1 ~ 8 part of binding agent, 0.1 ~ 2 part, barium sulfate, 0.01 ~ 2 part, liberation of hydrogen inhibitor, 1 ~ 4 part of humic acid, 5 ~ 15 parts of red lead, 12 ~ 21 parts, water, 0.1 ~ 0.2 part, short fiber and graphene combination electrode material;
Wherein, described graphene combination electrode comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of described nitrogen-doped graphene sheet interlayer, and the mass ratio of described nitrogen-doped graphene and lead sulfate is 1: 10 ~ 20.
7. plumbous carbon battery cathode lead plaster according to claim 6, is characterized in that,
Described binding agent is polytetrafluoroethylene, sodium carboxymethylcellulose or butadiene-styrene rubber;
Described liberation of hydrogen inhibitor is indium oxide, bismuth oxide, stearic acid, barium stearate, bismuth metal or samarium metal;
Described short fiber is selected from nylon, acrylic fibers or terylene.
8. plumbous carbon battery cathode lead plaster according to claim 6, is characterized in that, the apparent density of described plumbous carbon battery cathode lead plaster is 3.5g/mL ~ 4.5g/mL.
9. a preparation method for plumbous carbon battery cathode lead plaster, is characterized in that, comprises the steps:
By mass parts, 0.1 ~ 0.2 part, 100 parts, lead powder, 0.1 ~ 2 part, barium sulfate, 0.01 ~ 2 part, liberation of hydrogen inhibitor, 1 ~ 10 part of graphene combination electrode material, 1 ~ 4 part of humic acid, 5 ~ 15 parts of red lead, short fiber is mixed to get to mixture, stir 10 minutes ~ 20 minutes;
By mass parts, 12 ~ 21 parts, water is poured in described mixture and obtained slurry, stir 10 minutes ~ 20 minutes;
By mass parts, under agitation, 4 ~ 100 parts, sulfuric acid is added in described slurry, stir 10 minutes ~ 20 minutes; And
By mass parts, in the described slurry that adds sulfuric acid, add 0.1 ~ 8 part of binding agent, stir 5 minutes ~ 20 minutes, obtain plumbous carbon battery cathode lead plaster;
Wherein, described graphene combination electrode comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of described nitrogen-doped graphene sheet interlayer, and the mass ratio of described nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
10. a plumbous carbon battery, comprise battery container and be contained in positive pole, negative pole and the electrolyte in described battery container, it is characterized in that, described negative pole comprises collector and be coated on the plumbous carbon battery cathode lead plaster on described collector, and described plumbous carbon battery cathode lead plaster comprises the following component by mass parts:
1 ~ 10 part of 100 parts, lead powder, 4 ~ 100 parts, sulfuric acid, 0.1 ~ 8 part of binding agent, 0.1 ~ 2 part, barium sulfate, 0.01 ~ 2 part, liberation of hydrogen inhibitor, 1 ~ 4 part of humic acid, 5 ~ 15 parts of red lead, 12 ~ 21 parts, water, 0.1 ~ 0.2 part, short fiber and graphene combination electrode material; Wherein, described graphene combination electrode material comprises nitrogen-doped graphene and is adsorbed in the lead sulfate of described nitrogen-doped graphene sheet interlayer, and the mass ratio of described nitrogen-doped graphene and lead sulfate is 1:10 ~ 20.
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Application publication date: 20140326 |