CN108123103A - It is graphitized activated carbon base compound additive and preparation and lead carbon battery cathode and application - Google Patents
It is graphitized activated carbon base compound additive and preparation and lead carbon battery cathode and application Download PDFInfo
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- CN108123103A CN108123103A CN201611062085.1A CN201611062085A CN108123103A CN 108123103 A CN108123103 A CN 108123103A CN 201611062085 A CN201611062085 A CN 201611062085A CN 108123103 A CN108123103 A CN 108123103A
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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
- H01M16/00—Structural combinations of different types of electrochemical generators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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- 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
- H01M4/362—Composites
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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
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of graphitization activated carbon base compound additive and its preparation and application, the additive is the graphitization active carbon particle containing metallic element, and 0.1 50wt% is the carbon with graphite-structure in charcoal particle；The specific surface area of active carbon particle is 100 3000m2/ g, electrical conductivity are 0.01 100S/cm；Wherein metallic element is the one or two or more kinds in Sn, Pb, Bi, Ce, In, Zn, and content is 0.01~30wt% in additive.Graphitization activated carbon according to the present invention has charge and discharge invertibity, charge and discharge circulation life and the charge acceptance higher than traditional lead acid batteries cathode as lead carbon battery cathode prepared by additive.
Description
Technical field
The invention belongs to lead carbon battery technical fields, and in particular to a kind of part graphitization activated carbon base compound additive
Composition, preparation method and fills the application of the additive cathode in lead carbon battery.
Background technology
Lead carbon battery is a kind of is combined ultracapacitor with lead-acid accumulator and the new type of energy storage device that forms.Plumbic acid
Accumulator is improved the performance of battery, as pulsed power so as to compensate for common valve as the energy, ultracapacitor
Control lead-acid battery cannot tackle the deficiency of various complicated use conditions.In lead carbon battery, ultracapacitor and plumbic acid electricity
Combination integrates within the energy storage mode of two kinds of pond, special additional electronic control circuit is not required so that the size of battery obtains
Control is arrived, system is simplified, so as to reduce energy storage cost.
Interior mixed type lead carbon battery refers to mix a small amount of carbon material in lead cathode and its performance is made to be improved and the service life
Obtain extended lead-acid accumulator.Which kind of carbon material to be adapted as the additive of NAM on, although having more research,
But by the end of there is no unified conclusion at present.The conclusion difference that different researchers draw is larger, even conflicting.Not similar shape
The effect that graphite, carbon black and the activated carbon of state promote lead carbon battery cathode performance has been reported that.Such as Spence observes addition
The cathode performance of flake graphite is best, and Valenciano then has found that incorporation flake graphite can reduce the performance of cathode.Shiomi
Etc. thinking carbon in PbSO4Conductive network is formed between crystal, so that the charge acceptance of negative plate gets a promotion.Ohmae etc.
Think that high conductivity carbon material is added in NAM the sulfation process that can delay, i.e. the carbon material as conductor inhibits negative
It insulate in pole plate with lead, the PbSO that cannot be reduced in charging process4The generation of crystal.Boden etc., which is observed, passes through elimination
PbSO4The accumulation that is generated in negative terminal surface and extended the service life of battery.Pavlov thought in charging process, PbSO4
Lead and carbon of the reduction in NAM surface it is parallel.So the effect of carbon is the electrochemical surface area improved in cathode, from
And make charging more complete, it is improved the capacity of electrode.In addition, carbon material also acts as the effect for reducing NAM apertures.Once hole
Footpath is reduced to less than 1.5 μm, and the process of sulfuric acid toward pore diffusion will be restricted, will generate in operation PbO rather than
PbSO4。
Carbon material is introduced in lead-acid battery cathode, the sulfation except that can slow down cathode improves the cycling of battery
Outside service life, also because it can improve the electric conductivity of discharge condition electrode, capacitance characteristic is introduced, so as to improve electricity to a certain extent
The charge acceptance of pole.
For the carbon material of lead carbon battery, in particular for the carbon material of interior mixed type lead carbon battery, except needing that there is height
Specific surface area outside, also there is certain electron conduction.Big surface area can be precipitated for sulphate crystal and provide activity
Position, and high electron conduction can promote the reduction reaction of lead sulfate, the two collective effect can slow down the sulfate of cathode
Change, further improve the charge acceptance of battery.
Commercial activated charcoal, the specific surface area of particularly capacitance carbon is higher, but electron conduction is relatively low, it is impossible to meet lead
The demand of carbon battery.A certain proportion of conductive black is mixed in activated carbon, absorbent charcoal material can be improved to a certain extent
Electronic conduction ability.Since conductive black and activated carbon are mechanical mixture, it is impossible to change the electronics inside active carbon particle and lead
Logical ability.
The content of the invention
In order to solve the above technical problems, the present invention proposes a kind of to be done lead carbon battery cathode using part graphitization activated carbon and added
Add the technology path of agent, design a kind of metallic element and poison part graphitization activated carbon base cathode additive agent, wherein metallic poison
The purpose of change is that electrode evolving hydrogen reaction is made to be effectively suppressed.The compound additive is incorporated into cathode, it is intended to improve lead carbon
The cycle life and charge acceptance of battery.
It is as follows to reach the specific technical solution of the invention described above use：
A kind of graphitization activated carbon base compound additive, the additive are the graphitization activated carbon containing metallic element
, 0.1-50wt% is the carbon with graphite-structure in charcoal particle；The specific surface area of active carbon particle is 100-3000m2/ g, electricity
Conductance is 0.01-100S/cm；Wherein metallic element is the one or two or more kinds in Sn, Pb, Bi, Ce, In, Zn, in additive
Middle content is 0.01~30wt%.
A kind of preparation method for being graphitized activated carbon base compound additive, first by catalyzed graphitization method relatively low
At a temperature of in active carbon particle in-situ preparation graphite silk ribbon, catalyst therein is then removed by pickling and washing, finally
It is introduced into using infusion process using as the metal ion of liberation of hydrogen inhibitor in the graphitization activated carbon of preparation, by drying and roasting,
Obtain graphitization activated carbon base compound additive.Specifically comprise the following steps：
(1) transition metal soluble-salt is weighed, is added in solvent, is stirred well to and is completely dissolved, obtains transition metal
Soluble solution, the concentration of metal soluble-salt are controlled in 0.01~50wt%；
(2) disodium ethylene diamine tetraacetate (EDTA) is weighed, is added in solvent, is stirred well to and is completely dissolved, obtained
Metal salt solution is crossed, the concentration of EDTA is controlled in 0.01~50wt%；
(3) the prepared transition metal soluble salt solutions of step (1) are added in step (2) EDTA solution, stirred
0.1~500min makes metal ion be fully complexed by EDTA；The molar ratio of transition metal soluble-salt and EDTA are 1:1~1:
10
(4) activated carbon is added in step (3) solution, stirs 0.1~500min, obtain slurry；
(5) by step (4) slurries, dry 0.1~20h obtains desciccate at 30~200 DEG C, then by desciccate
Under inert atmosphere protection at 500~1000 DEG C roasting 0.1~for 24 hours；The addition of activated carbon in rate-determining steps (4), it is ensured that
The content of transition metal element is 0.01~50wt% in product of roasting；
(6) it is 1 in mass ratio:1~1:The product of roasting of step (5) is added to concentration as the dilute of 0.01~5mol/L by 50
In salpeter solution, stirring 0.1~for 24 hours, after whipping process, using deionized water centrifuge washing, upper strata is clear after centrifugation
Liquid pH value is neutrality, to remove transition metal ions therein；
(7) by neutral solution obtained by step (6) dry 0.1 at 30~200 DEG C~for 24 hours, obtain part graphitization activity
Charcoal；
(8) it is 1 according to the mass ratio of high overpotential of hydrogen evolution metallic element in final product and part graphitization activated carbon:100
~95:100, the high overpotential of hydrogen evolution metallic element soluble-salt of required corrresponding quality is weighed, then by high overpotential of hydrogen evolution gold
Belong to element soluble-salt to be dissolved in solvent, stirring is completely dissolved it, and it is molten to obtain high overpotential of hydrogen evolution metallic element soluble-salt
Liquid, the concentration of solution are controlled in 0.01mol/L between high overpotential of hydrogen evolution metallic element soluble-salt saturation solubility；
(9) part graphitization activated carbon is added in high overpotential of hydrogen evolution metallic element soluble salt solutions, stirring is equal
Even obtained part graphitization activated carbon and high overpotential of hydrogen evolution metallic element soluble-salt compound；Part graphitization activated carbon
Addition by high overpotential of hydrogen evolution metallic element in final product and part graphitization activated carbon mass ratio determine；In final product
The mass ratio of high overpotential of hydrogen evolution metallic element and part graphitization activated carbon is 1:100~95:100；
(10) sulfuric acid is added to by sulfuric acid and the amount needed for high overpotential of hydrogen evolution metallic element soluble-salt completely reaction
Carbon material that step (9) obtains in high overpotential of hydrogen evolution metallic element dissoluble lead salt composite, be sufficiently stirred make sulfuric acid with
High overpotential of hydrogen evolution metallic element soluble-salt reacts completely；The density of sulfuric acid used is 1.05~1.85g/cm3；
(11) step (10) is obtained product at 30~200 DEG C to be dried, grinding is uniform, obtains high overpotential of hydrogen evolution
The part graphitization activated carbon that metallic element is modified, that is, be graphitized activated carbon base compound additive.
Soluble transition metal salt in step (1) is one or two or more kinds of nitrate, the acetic acid in Fe, Co, Ni
One or two or more kinds in salt, alkoxide.
Solvent in step (1), (2) and (8) is water, the one or two or more kinds in methanol, ethyl alcohol.
High overpotential of hydrogen evolution metallic element in step (8), (9), (10) and (11) is Sn, Pb, Bi, Ce, In, in Zn
It is one or two or more kinds of；Nitrate that high overpotential of hydrogen evolution metallic element soluble-salt is, acetate, one kind in alkoxide or two
Kind or more.
The composite negative pole is prepared using following steps,
(1) graphitization activated carbon base compound additive, auxiliary material, staple fiber and lead powder are pressed into (0.1~30):(0.1-20):
(0.1~10):(50~99) mass ratio is uniformly mixed；
(2) water and sulfuric acid are added in into the mixture that step (12) obtains, is sufficiently stirred and prepares lead plaster；The density of sulfuric acid is
1.05~1.85g/cm3, addition accounts for the 1~30% of mixture quality, the addition of water account for mixture quality 0.5~
50%；
(3) lead plaster is scratched onto grid, it is cured to be dried to obtain lead carbon battery composite negative pole life pole piece；It is living on raw pole piece
Property substance thickness be 0.1~10mm；Solidification temperature is 10~100 DEG C, and relative humidity is 10~100%, hardening time 1-
50h；Drying temperature is 10~200 DEG C, and relative humidity is 0~80%, drying time 1-50h；Wherein, the staple fiber is
One or both of polypropylene fibre, acrylic fiber, fibre length are 1~10mm；Auxiliary material is one in barium sulfate, humic acid
Kind or two kinds of mixtures.
Application of the lead carbon battery composite negative pole in lead carbon battery.
Beneficial effects of the present invention：
(1) metallic element according to the present invention, which poisons part graphitization activated carbon, not only has high specific surface area, but also tool
There is high electron conduction, as lead carbon battery cathode additive agent in use, the micropore surface in active carbon with high specific surface area can
Precipitation for lead sulfate crystal grain in discharge process provides active sites, is conducive to limit further growing up for lead sulfate crystal grain, so as to
It prevents the sulfation of the lead carbon battery cathode during high current charge-discharge, reduces the internal resistance of lead carbon battery；Active carbon particle
Middle graphite silk ribbon has high electric conductivity, can provide path for electron-transport, is conducive to improve the speed of electrode charge and discharge reaction
Degree and invertibity.In addition, the presence of high overpotential of hydrogen evolution metallic element, the evolving hydrogen reaction that can be occurred with inhibitory activity carbon surface,
Be conducive to improve the performance and cycle life of electrode.
(2) the dopand metals element prepared using method involved in the present invention poisons the lead carbon electricity of part graphitization activated carbon
Pond cathode has charge and discharge invertibity, charge and discharge circulation life and the charge acceptance higher than traditional lead acid batteries.
(3) metallic element according to the present invention poisons part graphitization active charcoal preparing process and equipment is simple, easily
In realization scale industrial production.
Description of the drawings
Fig. 1 admixtures 1.5wt% poisons the lead carbon electricity of graphitization activated carbon (calcination temperature is 800 DEG C, roasting time 2h)
Linear polarisation curves under chemical property (a) the potential scanning speed 5mV/s of pond cathode；(b) under potential scanning speed 5mV/s
Cyclic voltammetry curve；
Fig. 2 admixtures 1.5wt% poisons the lead carbon electricity of graphitization activated carbon (calcination temperature is 900 DEG C, roasting time 2h)
Linear polarisation curves under chemical property (a) the potential scanning speed 5mV/s of pond cathode；(b) under potential scanning speed 5mV/s
Cyclic voltammetry curve；
Fig. 3 admixtures 1.5wt% poisons the lead carbon electricity of graphitization activated carbon (calcination temperature is 800 DEG C, roasting time 5h)
Linear polarisation curves under chemical property (a) the potential scanning speed 5mV/s of pond cathode；(b) under potential scanning speed 5mV/s
Cyclic voltammetry curve；
Fig. 4 admixtures 2.0wt% poisons the lead carbon electricity of graphitization activated carbon (calcination temperature is 800 DEG C, roasting time 2h)
Linear polarisation curves under chemical property (a) the potential scanning speed 5mV/s of pond cathode；(b) under potential scanning speed 5mV/s
Cyclic voltammetry curve；
Chemical property (a) potential scanning speed of the lead carbon battery cathode of Fig. 5 admixture unmodified activated carbons of 1.5wt%
Linear polarisation curves under 5mV/s；(b) cyclic voltammetry curve under potential scanning speed 5mV/s；
Linear polarisation curves under chemical property (a) the potential scanning speed 5mV/s of Fig. 6 lead-acid battery cathodes；(b) it is electric
Cyclic voltammetry curve under bit scan speed 5mV/s.
Specific embodiment
The following examples will be further described the present invention, but right not thereby limiting the invention will
It asks.
The specific preparation process and characterizing method for the lead carbon battery composite negative pole that following embodiments are related to are as follows：
(1) by obtained high overpotential of hydrogen evolution metallic element poison part graphitization activated carbon, auxiliary material and staple fiber according to
Certain ratio is added in lead powder, is premixed using homogenizer, obtains lead carbon battery cathode powder；
(2) 0.1~10% deionized water is quickly added in into cathode powder while stirring, after stirring evenly, while stirring
0.1~10% sulfuric acid is slowly added to, is stirred evenly, lead plaster is made.The density domination of lead plaster is in 4.0-5.0g/cm3；
(3) lead plaster is scratched onto stereotype grid, is cured and dried under certain temperature and humidity.Solidification temperature 40
DEG C, humidity 80%, hardening time 20h；Drying temperature is 80 DEG C, and the time is for 24 hours；
(4) the cathode green plate prepared is formed full battery with anode green plate to be melted into；
(5) structure three-electrode system characterizes the chemical property of cathode after chemical conversion, is done using mercury/mercuric sulfate electrode
Reference electrode, characterizing method used include linear scan and cyclic voltammetric.Potential window is to open used by linear scan is tested
Road voltage (OCV) arrives -1.5V, and potential window is 0 to -1.5V used by cyclic voltammetry.
Embodiment 1
Analytically pure nickel nitrate 0.2g is weighed, is added in 10mL deionized waters, is stirred well to and is completely dissolved, obtain nitre
Sour nickel solution.Analytically pure disodium ethylene diamine tetraacetate (EDTA) 0.2816g is weighed, is added in 20mL deionized waters, fully
Stirring obtains EDTA solution to being completely dissolved.Prepared nickel nitrate solution is added in EDTA solution, 30min is stirred, makes
Nickel ion is fully complexed by EDTA.Then 10g activated carbons are added in above-mentioned solution, 30min are stirred, by gained slurries 85
20h is dried at DEG C, by drying gained powder in N22h is roasted at 800 DEG C in protective atmosphere, obtains part graphitization activated carbon.It takes
1.5g parts graphitization activated carbon, is added in the dilute nitric acid solution that 150ml concentration is 1mol/L, stirs 16h, carry out pickling.
Deionized water centrifuge washing is used after whipping process 3-6 times, supernatant liquor pH value reaches 7.0 after centrifugation, by gained
Neutral solution dries 20h at 85 DEG C and obtains the graphitization activated carbon of the part after pickling.It weighs 0.078g plumbi nitras and is added to 4ml
It in deionized water, stirs to abundant dissolving, obtains lead nitrate solution, weigh the graphitization activated carbon 1g of the part after pickling and be added to
Slurries are uniformly mixing to obtain in above-mentioned lead nitrate solution, density is then slowly added dropwise while stirring into the slurries as 1.245g/
Gained slurries are dried 20h at 85 DEG C and obtain the graphitization work of the part after lead sulfate poisons by the sulfuric acid 0.069g of ml (25 DEG C)
Property charcoal front axle shell.By above-mentioned front axle shell in N22h is roasted at 210 DEG C in protective atmosphere, the part graphitization activity after being poisoned
Charcoal.Part graphitization activated carbon after 10g lead powder, 0.15g are poisoned, 0.14g barium sulfate, poly- third that 0.005g length is 5mm
Alkene staple fiber is premixed with homogenizer.1.4g deionized waters are added in into the powder of premix while stirring.It stirs evenly
Afterwards, the sulfuric acid 0.71g that density is 1.40g/mL (25 DEG C) is slowly added dropwise while stirring, the temperature of control material is not higher than 65 DEG C,
Persistently stirring 10min obtains lead plaster.By on lead plaster blade coating to metallic lead grid, lead carbon battery cathode is obtained through dry solidification.Gu
Change 40 DEG C of temperature, humidity 80%, hardening time 20h；Drying temperature is 80 DEG C, and the time is for 24 hours.Using identical technique system
Standby lead-acid battery anode.It is worked electrode with the lead carbon battery cathode of above-mentioned preparation, lead-acid battery anode is made to electrode, saturation sulphur
Sour mercury electrode makees reference electrode and forms three-electrode system, and electrochemical Characterization is carried out to the lead carbon battery cathode of preparation.Linear scan
The potential window of polarization curve is open circuit potential to -1.5V.The potential window of cyclic voltammetry is 0 to -1.5V.Shown in Fig. 1
For the Electrochemical Characterization for being graphitized the lead carbon battery cathode of activated carbon additive using the part after 1.5wt% poisons is filled
As a result.It is compared with lead-acid battery cathode (comparative example 1, Fig. 5), the lead carbon battery cathode that admixture 1.5wt% lead sulfates poison has
Higher charge and discharge is electroactive.It compares, mixes with the lead carbon battery cathode (comparative example 2, Fig. 6) of the admixture unmodified activated carbons of 1.5wt%
Add the lead carbon battery cathode that 1.5wt% lead sulfates poison that there is lower liberation of hydrogen electric current.
Embodiment 2
Analytically pure nickel nitrate 0.2g is weighed, is added in 10mL deionized waters, is stirred well to and is completely dissolved, obtain nitre
Sour nickel solution.Analytically pure disodium ethylene diamine tetraacetate (EDTA) 0.2816g is weighed, is added in 20mL deionized waters, fully
Stirring obtains EDTA solution to being completely dissolved.Prepared nickel nitrate solution is added in EDTA solution, 30min is stirred, makes
Nickel ion is fully complexed by EDTA.Then 10g activated carbons are added in above-mentioned solution, 30min are stirred, by gained slurries 85
20h is dried at DEG C, by drying gained powder in N22h is roasted at 900 DEG C in protective atmosphere, obtains part graphitization activated carbon.It takes
1.5g parts graphitization activated carbon, is added in the dilute nitric acid solution that 150ml concentration is 1mol/L, stirs 16h, carry out pickling,
Deionized water centrifuge washing is used after whipping process 3-6 times, supernatant liquor pH value reaches 7.0 after centrifugation, by gained
Neutral solution dries 20h at 85 DEG C and obtains the graphitization activated carbon of the part after pickling.It weighs 0.078g plumbi nitras and is added to 4ml
It in deionized water, stirs to abundant dissolving, obtains lead nitrate solution, weigh the graphitization activated carbon 1g of the part after pickling and be added to
Slurries are uniformly mixing to obtain in above-mentioned lead nitrate solution, density is then slowly added dropwise while stirring into the slurries as 1.245g/
Gained slurries are dried 20h at 85 DEG C and obtain the graphitization work of the part after lead sulfate poisons by the sulfuric acid 0.069g of ml (25 DEG C)
Property charcoal front axle shell.By above-mentioned front axle shell in N22h is roasted at 210 DEG C in protective atmosphere, the part graphitization activity after being poisoned
Charcoal.Part graphitization activated carbon after 10g lead powder, 0.15g are poisoned, 0.14g barium sulfate, poly- third that 0.005g length is 5mm
Alkene staple fiber is premixed with homogenizer.1.4g deionized waters are added in into the powder of premix while stirring.It stirs evenly
Afterwards, the sulfuric acid 0.71g that density is 1.40g/mL (25 DEG C) is slowly added dropwise while stirring, the temperature of control material is not higher than 65 DEG C,
Persistently stirring 10min obtains lead plaster.By on lead plaster blade coating to metallic lead grid, lead carbon battery cathode is obtained through dry solidification.Gu
Change 40 DEG C of temperature, humidity 80%, hardening time 20h；Drying temperature is 80 DEG C, and the time is for 24 hours.Using identical technique system
Standby lead-acid battery anode.It is worked electrode with the lead carbon battery cathode of above-mentioned preparation, lead-acid battery anode is made to electrode, saturation sulphur
Sour mercury electrode makees reference electrode and forms three-electrode system, and electrochemical Characterization is carried out to the lead carbon battery cathode of preparation.Linear scan
The potential window of polarization curve is open circuit potential to -1.5V.The potential window of cyclic voltammetry is 0 to -1.5V.Shown in Fig. 2
For the Electrochemical Characterization for being graphitized the lead carbon battery cathode of activated carbon additive using the part after 1.5wt% poisons is filled
As a result.It is compared with lead-acid battery cathode (comparative example 1, Fig. 5), the lead carbon battery cathode that admixture 1.5wt% lead sulfates poison has
Higher charge and discharge is electroactive.It compares, mixes with the lead carbon battery cathode (comparative example 2, Fig. 6) of the admixture unmodified activated carbons of 1.5wt%
Add the lead carbon battery cathode that 1.5wt% lead sulfates poison that there is lower liberation of hydrogen electric current.
Embodiment 3
Analytically pure nickel nitrate 0.2g is weighed, is added in 10mL deionized waters, is stirred well to and is completely dissolved, obtain nitre
Sour nickel solution.Analytically pure disodium ethylene diamine tetraacetate (EDTA) 0.2816g is weighed, is added in 20mL deionized waters, fully
Stirring obtains EDTA solution to being completely dissolved.Prepared nickel nitrate solution is added in EDTA solution, 30min is stirred, makes
Nickel ion is fully complexed by EDTA.Then 10g activated carbons are added in above-mentioned solution, 30min are stirred, by gained slurries 85
20h is dried at DEG C, by drying gained powder in N25h is roasted at 800 DEG C in protective atmosphere, obtains part graphitization activated carbon.It takes
1.5g parts graphitization activated carbon, is added in the dilute nitric acid solution that 150ml concentration is 1mol/L, stirs 16h, carry out pickling,
Deionized water centrifuge washing is used after whipping process 3-6 times, supernatant liquor pH value reaches 7.0 after centrifugation, by gained
Neutral solution dries 20h at 85 DEG C and obtains the graphitization activated carbon of the part after pickling.It weighs 0.078g plumbi nitras and is added to 4ml
It in deionized water, stirs to abundant dissolving, obtains lead nitrate solution, weigh the graphitization activated carbon 1g of the part after pickling and be added to
Slurries are uniformly mixing to obtain in above-mentioned lead nitrate solution, density is then slowly added dropwise while stirring into the slurries as 1.245g/
Gained slurries are dried 20h at 85 DEG C and obtain the graphitization work of the part after lead sulfate poisons by the sulfuric acid 0.069g of ml (25 DEG C)
Property charcoal front axle shell.By above-mentioned front axle shell in N22h is roasted at 210 DEG C in protective atmosphere, the part graphitization activity after being poisoned
Charcoal.Part graphitization activated carbon after 10g lead powder, 0.15g are poisoned, 0.14g barium sulfate, poly- third that 0.005g length is 5mm
Alkene staple fiber is premixed with homogenizer.1.4g deionized waters are added in into the powder of premix while stirring.It stirs evenly
Afterwards, the sulfuric acid 0.71g that density is 1.40g/mL (25 DEG C) is slowly added dropwise while stirring, the temperature of control material is not higher than 65 DEG C,
Persistently stirring 10min obtains lead plaster.By on lead plaster blade coating to metallic lead grid, lead carbon battery cathode is obtained through dry solidification.Gu
Change 40 DEG C of temperature, humidity 80%, hardening time 20h；Drying temperature is 80 DEG C, and the time is for 24 hours.Using identical technique system
Standby lead-acid battery anode.It is worked electrode with the lead carbon battery cathode of above-mentioned preparation, lead-acid battery anode is made to electrode, saturation sulphur
Sour mercury electrode makees reference electrode and forms three-electrode system, and electrochemical Characterization is carried out to the lead carbon battery cathode of preparation.Linear scan
The potential window of polarization curve is open circuit potential to -1.5V.The potential window of cyclic voltammetry is 0 to -1.5V.Shown in Fig. 3
For the Electrochemical Characterization for being graphitized the lead carbon battery cathode of activated carbon additive using the part after 1.5wt% poisons is filled
As a result.It is compared with lead-acid battery cathode (comparative example 1, Fig. 5), the lead carbon battery cathode that admixture 1.5wt% lead sulfates poison has
Higher charge and discharge is electroactive.It compares, mixes with the lead carbon battery cathode (comparative example 2, Fig. 6) of the admixture unmodified activated carbons of 1.5wt%
Add the lead carbon battery cathode that 1.5wt% lead sulfates poison that there is lower liberation of hydrogen electric current.
Embodiment 4
Analytically pure nickel nitrate 0.2g is weighed, is added in 10mL deionized waters, is stirred well to and is completely dissolved, obtain nitre
Sour nickel solution.Analytically pure disodium ethylene diamine tetraacetate (EDTA) 0.2816g is weighed, is added in 20mL deionized waters, fully
Stirring obtains EDTA solution to being completely dissolved.Prepared nickel nitrate solution is added in EDTA solution, 30min is stirred, makes
Nickel ion is fully complexed by EDTA.Then 10g activated carbons are added in above-mentioned solution, 30min are stirred, by gained slurries 85
20h is dried at DEG C, by drying gained powder in N22h is roasted at 800 DEG C in protective atmosphere, obtains part graphitization activated carbon.It takes
1.5g parts graphitization activated carbon, is added in the dilute nitric acid solution that 150ml concentration is 1mol/L, stirs 16h, carry out pickling,
Deionized water centrifuge washing is used after whipping process 3-6 times, supernatant liquor pH value reaches 7.0 after centrifugation, by gained
Neutral solution dries 20h at 85 DEG C and obtains the graphitization activated carbon of the part after pickling.It weighs 0.078g plumbi nitras and is added to 4ml
It in deionized water, stirs to abundant dissolving, obtains lead nitrate solution, weigh the graphitization activated carbon 1g of the part after pickling and be added to
Slurries are uniformly mixing to obtain in above-mentioned lead nitrate solution, density is then slowly added dropwise while stirring into the slurries as 1.245g/
Gained slurries are dried 20h at 85 DEG C and obtain the graphitization work of the part after lead sulfate poisons by the sulfuric acid 0.069g of ml (25 DEG C)
Property charcoal front axle shell.By above-mentioned front axle shell in N22h is roasted at 210 DEG C in protective atmosphere, the part graphitization activity after being poisoned
Charcoal.Part graphitization activated carbon after 10g lead powder, 0.2g are poisoned, 0.14g barium sulfate, the polypropylene that 0.005g length is 5mm
Staple fiber is premixed with homogenizer.1.4g deionized waters are added in into the powder of premix while stirring.After stirring evenly,
The sulfuric acid 0.71g that density is 1.40g/mL (25 DEG C) is slowly added dropwise while stirring, the temperature of control material continues not higher than 65 DEG C
Stirring 10min obtains lead plaster.By on lead plaster blade coating to metallic lead grid, lead carbon battery cathode is obtained through dry solidification.Cure temperature
40 DEG C of degree, humidity 80%, hardening time 20h；Drying temperature is 80 DEG C, and the time is for 24 hours.Lead is prepared using identical technique
Sour anode.It is worked electrode with the lead carbon battery cathode of above-mentioned preparation, lead-acid battery anode is made to electrode, saturation mercuric sulfate
Electrode makees reference electrode and forms three-electrode system, and electrochemical Characterization is carried out to the lead carbon battery cathode of preparation.Linear scan polarizes
The potential window of curve is open circuit potential to -1.5V.The potential window of cyclic voltammetry is 0 to -1.5V.Fig. 4, which is shown, to be adopted
The Electrochemical Characterization knot of the lead carbon battery cathode of part graphitization activated carbon additive after being poisoned with admixture 1.5wt%
Fruit.It is compared with lead-acid battery cathode (to example 1, Fig. 5), the lead carbon battery cathode that admixture 1.5wt% lead sulfates poison has higher
Charge and discharge it is electroactive.It compares, fills with the lead carbon battery cathode (comparative example 2, Fig. 6) of the admixture unmodified activated carbons of 1.5wt%
The lead carbon battery cathode that 1.5wt% lead sulfates poison has lower liberation of hydrogen electric current.
Comparative example 1
10g lead powder, 0.14g barium sulfate, the polypropene staple that 0.005g length is 5mm are carried out in advance with homogenizer
It is mixed.1.4g deionized waters are added in into the powder of premix while stirring.After stirring evenly, density is slowly added dropwise while stirring is
The sulfuric acid 0.71g of 1.40g/mL (25 DEG C), the temperature of control material persistently stir 10min and obtain lead plaster not higher than 65 DEG C.By lead
Cream is scratched onto metallic lead grid, and lead-acid battery cathode is obtained through dry solidification.40 DEG C of solidification temperature, humidity 80% cure
Time is 20h；Drying temperature is 80 DEG C, and the time is for 24 hours.Lead-acid battery anode is prepared using identical technique.With above-mentioned preparation
Cathode work electrode, anode is made to electrode, and saturation mercuric sulfate electrode makees reference electrode and forms three-electrode system, to preparation
Lead carbon battery cathode carries out electrochemical Characterization.The potential window of linear scan polarization curve is open circuit potential to -1.5V.Xun Huan volt
The potential window of peace test is 0 to -1.5V.Fig. 5 show the Electrochemical Characterization result of lead-acid battery cathode.
Comparative example 2
10g lead powder, the untreated activated carbons of 0.15g, 0.14g barium sulfate, 0.005g length is short for the polypropylene of 5mm
Fiber is premixed with homogenizer.1.4g deionized waters are added in into the powder of premix while stirring.After stirring evenly, side
The sulfuric acid 0.71g that density is 1.40g/mL (25 DEG C) is slowly added dropwise in stirring side, and the temperature of control material is persistently stirred not higher than 65 DEG C
It mixes 10min and obtains lead plaster.By on lead plaster blade coating to metallic lead grid, lead carbon battery cathode is obtained through dry solidification.Solidification temperature
40 DEG C, humidity 80%, hardening time 20h；Drying temperature is 80 DEG C, and the time is for 24 hours.Plumbic acid is prepared using identical technique
Anode.It is worked electrode with the lead carbon battery cathode of above-mentioned preparation, lead-acid battery anode is made to electrode, saturation mercuric sulfate electricity
Pole makees reference electrode and forms three-electrode system, and electrochemical Characterization is carried out to the lead carbon battery cathode of preparation.Linear scan polarization is bent
The potential window of line is open circuit potential to -1.5V.The potential window of cyclic voltammetry is 0 to -1.5V.Fig. 6 show use
Fill the Electrochemical Characterization result of the lead carbon battery cathode of the unprocessed activated carbons of 1.5wt%.
Claims (7)
1. a kind of graphitization activated carbon base compound additive, which is characterized in that the additive is the graphite containing metallic element
Change active carbon particle, 0.1-50wt% is the carbon with graphite-structure in charcoal particle；The specific surface area of active carbon particle is 100-
3000m2/ g, electrical conductivity 0.01-100S/cm；Wherein metallic element for one kind in Sn, Pb, Bi, Ce, In, Zn or two kinds with
On, content is 0.01~30wt% in additive.
2. a kind of preparation method for being graphitized activated carbon base compound additive, includes the following steps：
(1) transition metal soluble-salt is weighed, is added in solvent, is stirred well to and is completely dissolved, it is solvable to obtain transition metal
Property solution, the concentration of metal soluble-salt controlled in 0.01~50wt%；
(2) disodium ethylene diamine tetraacetate (EDTA) is weighed, is added in solvent, is stirred well to and is completely dissolved, obtains transition gold
Belong to salting liquid, the concentration of EDTA is controlled in 0.01~50wt%；
(3) the prepared transition metal soluble salt solutions of step (1) are added in step (2) EDTA solution, stirring 0.1~
500min makes metal ion be fully complexed by EDTA；The molar ratio of transition metal soluble-salt and EDTA are 1:1~1:10；
(4) activated carbon is added in step (3) solution, stirs 0.1~500min, obtain slurry；
(5) by step (4) slurries, dry 0.1~20h obtains desciccate at 30~200 DEG C, then by desciccate lazy
Property atmosphere protection under at 500~1000 DEG C roasting 0.1~for 24 hours；The addition of activated carbon in rate-determining steps (4), it is ensured that roasting
The content of transition metal element is 0.01~50wt% in product；
(6) it is 1 in mass ratio:1~1:50 are added to the product of roasting of step (5) dust technology that concentration is 0.01~5mol/L
In solution, stirring 0.1~for 24 hours, after whipping process, using deionized water centrifuge washing, the supernatant liquor pH after centrifugation
It is worth for neutrality, to remove transition metal ions therein；
(7) by neutral solution obtained by step (6) dry 0.1 at 30~200 DEG C~for 24 hours, obtain part graphitization activated carbon；
(8) it is 1 according to the mass ratio of high overpotential of hydrogen evolution metallic element in final product and part graphitization activated carbon:100~95:
100, the high overpotential of hydrogen evolution metallic element soluble-salt of required corrresponding quality is weighed, then by high overpotential of hydrogen evolution metallic element
Soluble-salt is dissolved in solvent, and stirring is completely dissolved it, obtains high overpotential of hydrogen evolution metallic element soluble salt solutions, solution
Concentration control in 0.01mol/L between high overpotential of hydrogen evolution metallic element soluble-salt saturation solubility；
(9) part graphitization activated carbon is added in high overpotential of hydrogen evolution metallic element soluble salt solutions, stirred evenly
Part graphitization activated carbon and the high overpotential of hydrogen evolution metallic element soluble-salt compound arrived；Part graphitization activated carbon adds
Enter amount to be determined by the mass ratio of high overpotential of hydrogen evolution metallic element in final product and part graphitization activated carbon；High analysis in final product
Hydrogen overpotential metallic element and the mass ratio of part graphitization activated carbon are 1:100~95:100；
(10) sulfuric acid is added to step by the amount needed for the reaction completely of sulfuric acid and high overpotential of hydrogen evolution metallic element soluble-salt
(9) carbon material obtained makes sulfuric acid be analysed with high in high overpotential of hydrogen evolution metallic element dissoluble lead salt composite, being sufficiently stirred
Hydrogen overpotential metallic element soluble-salt reacts completely；The density of sulfuric acid used is 1.05~1.85g/cm3；
(11) step (10) is obtained product at 30~200 DEG C to be dried, grinding is uniform, obtains high overpotential of hydrogen evolution metal
Element modified part graphitization activated carbon, that is, be graphitized activated carbon base compound additive.
3. preparation method described in accordance with the claim 2, it is characterised in that：Soluble transition metal salt in step (1) is Fe,
The one or two or more kinds in one or two or more kinds of nitrate, acetate, alkoxide in Co, Ni.
4. preparation method described in accordance with the claim 2, it is characterised in that：Solvent in step (1), (2) and (8) is water, first
One or two or more kinds in alcohol, ethyl alcohol.
5. preparation method described in accordance with the claim 2, it is characterised in that：High liberation of hydrogen in step (8), (9), (10) and (11)
Overpotential metallic element is Sn, Pb, Bi, Ce, In, the one or two or more kinds in Zn；High overpotential of hydrogen evolution metallic element is solvable
One or two or more kinds in nitrate that property salt is, acetate, alkoxide.
6. a kind of lead carbon battery composite negative pole for including compound additive described in claim 1, it is characterised in that：The Compound Negative
Pole is prepared using following steps,
(1) graphitization activated carbon base compound additive, auxiliary material, staple fiber and lead powder are pressed into (0.1~30):(0.1-20):(0.1
~10):(50~99) mass ratio is uniformly mixed；
(2) water and sulfuric acid are added in into the mixture that step (12) obtains, is sufficiently stirred and prepares lead plaster；The density of sulfuric acid is 1.05
~1.85g/cm3, addition accounts for the 1~30% of mixture quality, and the addition of water accounts for the 0.5~50% of mixture quality；
(3) lead plaster is scratched onto grid, it is cured to be dried to obtain lead carbon battery composite negative pole life pole piece；Active matter on raw pole piece
Matter thickness is 0.1~10mm；Solidification temperature is 10~100 DEG C, and relative humidity is 10~100%, hardening time 1-50h；It is dry
Dry temperature is 10~200 DEG C, and relative humidity is 0~80%, drying time 1-50h；Wherein, the staple fiber is polypropylene
One or both of fiber, acrylic fiber, fibre length are 1~10mm；Auxiliary material is barium sulfate, one kind in humic acid or two
Kind mixture.
7. a kind of application of the lead carbon battery composite negative pole in lead carbon battery described in claim 6.
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| CN111261847A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Hydrothermal synthesis method of lead-carbon battery electrode, electrode and application thereof |
| CN112436143A (en) * | 2020-11-06 | 2021-03-02 | 风帆有限责任公司 | Preparation method of negative electrode lead paste and negative electrode plate of lead-acid storage battery |
| CN112635761A (en) * | 2019-09-24 | 2021-04-09 | 广隆光电科技股份有限公司 | Negative electrode lead paste composition of lead-acid battery, negative plate and lead-acid battery |
| CN113948701A (en) * | 2020-07-17 | 2022-01-18 | 中国科学院大连化学物理研究所 | Activated carbon composite material and application thereof in lead-carbon battery |
| CN113948700A (en) * | 2020-07-17 | 2022-01-18 | 中国科学院大连化学物理研究所 | Monodisperse atomic cluster-activated carbon composite material and application thereof in lead-carbon battery |
| CN114497544A (en) * | 2020-11-12 | 2022-05-13 | 中国科学院大连化学物理研究所 | Additive-loaded activated carbon composite material and preparation and application thereof |
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| CN112635761A (en) * | 2019-09-24 | 2021-04-09 | 广隆光电科技股份有限公司 | Negative electrode lead paste composition of lead-acid battery, negative plate and lead-acid battery |
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| CN113948700B (en) * | 2020-07-17 | 2023-06-06 | 中国科学院大连化学物理研究所 | Monodisperse atomic cluster-activated carbon composite material and application thereof in lead carbon battery |
| CN112436143A (en) * | 2020-11-06 | 2021-03-02 | 风帆有限责任公司 | Preparation method of negative electrode lead paste and negative electrode plate of lead-acid storage battery |
| CN114497544A (en) * | 2020-11-12 | 2022-05-13 | 中国科学院大连化学物理研究所 | Additive-loaded activated carbon composite material and preparation and application thereof |
| CN114497544B (en) * | 2020-11-12 | 2023-10-13 | 中国科学院大连化学物理研究所 | Additive-loaded active carbon composite material and preparation and application thereof |
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