CN106941166B - A kind of lead titanium Si-C composite material and preparation method thereof - Google Patents
A kind of lead titanium Si-C composite material and preparation method thereof Download PDFInfo
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Abstract
A kind of lead titanium Si-C composite material and preparation method thereof, wherein lead titanium Si-C composite material is after being mixed by carbon material with silica, titanyl sulfate solution is added, the titanium Si-C composite material calcined under a nitrogen atmosphere after being washed with ammonia spirit, add lead salt solution, with acid solution wash, the lead sulfate-carbon-based material combination electrode material obtained after dry is mixed with metal oxide, and obtained in the surface of mixture injection silica.The lead titanium Si-C composite material has the advantages that improve electric conductivity, charge acceptance and charge-discharge magnification, can convert lead salt in active lead, lead salt crystalline solid is inhibited to increase and salinization；Lead titanium Si-C composite material binding force enhancing after in conjunction with lead, makes it keep some strength in charge and discharge process, will not loosely fall off because of rush of current；Overpotential of hydrogen evolution is improved, cathode is inhibited to lose hydrogen too early；Improve cycle life.
Description
Technical field
The present invention relates to electrochemical storage cell technical fields, and in particular to a kind of lead titanium Si-C composite material and its preparation side
Method.
Background technique
With the fast development of global economy and society, increasingly ecological environment is worsening simultaneously for shortage for the energy, because of this person
Increasingly pay attention to utilizing the renewable resources such as solar energy, wind energy.But the energy caused by solar energy, wind energy cannot directly simultaneously
Enter power grid for people production, live it is practical, need energy storage device first energy storage.
Currently, the field is common and the battery of relative maturity is broadly divided into lithium ion battery, flow battery, Ni-H cell
And lead-acid battery, and first three battery is compared, lead-acid battery still has biggish excellent in terms of cost, safety and low temperature discharge
Gesture, therefore so far, lead-acid battery still occupies most of share in many battery applications fields.But due to can
The fast development of the renewable sources of energy and smart grid proposes requirements at the higher level to energy-storage battery performance used, such as difference under PSOC
Charge-discharge performance, deep discharge circulation, frequent fast charging and discharging of multiplying power electric current etc., to this, traditional lead-acid battery can not
Meet current requirement.
Solar energy, wind power generation are more demanding to required energy-storage battery, it is desirable that in the charge and discharge of low range unsaturation and
It can be run for a long time in the biggish situation of depth of discharge, and restorative full charge cannot be carried out in time.Existing battery performance
Above-mentioned requirements can not be reached, therefore will lead to battery sulfuric acid oxidation, cathode premature failure, greatly reduce battery uses the longevity
Life.And the requirement for smart grid to required energy-storage battery be can be in the frequent fast charging and discharging of high current.
To meet above-mentioned requirements, Lam et al. has produced supercapacitor, and anode is conventional brown lead oxide pole plate, cathode
Including carbon electrode and lead electrode in parallel.The grid quantity that the supercapacitor uses is more, increases battery weight.
D.Pavlov et al. is added the materials such as active carbon, carbon black into common lead plaster, the superbattery that they do can 50%SOC,
Charge and discharge are carried out with 2C electric current under 3%DOD, but the battery is suitble to hybrid electric vehicle, and be not suitable for solar energy and wind energy to electricity
PSOC cycle life and the high rate performance requirement in pond.
For example, disclosing a kind of lead graphene composite material, it is noted that one application No. is 201210375260.8 invention
The preparation method of kind lead graphene composite material, can be used for improving battery by lead graphene composite material prepared by this method
Charge acceptance and HRPSOC (multiplying power part charged state) cycle life.
For another example, application No. is 201210548722.1 inventions, disclose a kind of modified activated carbon area load lead oxide,
The modified activated carbon is the active carbon modified using hydrogen inhibitor, and the hydrogen inhibitor is the oxidation for being supported on activated carbon surface
Lead, preparation process are first to be reused alkali using activated carbon adsorption lead ion for lead ion and be deposited on activated carbon surface, finally led to
Overheating Treatment makes lead hydroxide resolve into lead oxide, and is supported on activated carbon surface, and active carbon, lead salt and alkali pass through ball grinding method
It chemically reacts, then protects again under compression ring border through height processing preparation.The modified activated carbon specific capacitance can reach
145F/g。
For another example, application No. is 201110093953.3 inventions, disclose a kind of lead sulfate-graphene combination electrode material
Material, pulse charge and discharge cycles number is greater than 6000 times for the first time.
In conclusion these three composite materials all improve lead-acid battery cathode performance to some extent, but all only it is applicable in
Pulse charge and discharge cycles within the depth of discharge 3% under 50%SOC state.If being applied to recycle the longevity to battery PSOC
Life requires, and high rate performance and restores the more demanding solar energy of charge characteristic, the power generation of wind energy renewable resource and smart grid,
Advantage is difficult to play or not exist.Therefore it needs to research and develop a kind of composite material at present, can be improved the battery PSOC circulation longevity
Life enhances high rate performance and restores charge characteristic, to meet solar energy, the power generation of wind energy renewable resource and smart grid to energy storage
The requirement of battery.
Summary of the invention
The application provides a kind of lead titanium Si-C composite material and preparation method thereof, which had both been suitble to too
It is positive to be also applied for the frequent fast charging and discharging mode of smart grid with the low range unsaturation charge and discharge mode of wind energy.
According in a first aspect, providing a kind of lead titanium Si-C composite material in a kind of embodiment, lead titanium Si-C composite material is
After being mixed by carbon material with silica, titanyl sulfate solution is added, is calcined under a nitrogen atmosphere after being washed with ammonia spirit
The titanium Si-C composite material arrived, adds lead salt solution, and with acid solution wash, the lead sulfate-carbon-based material obtained after dry is multiple
Composite electrode material is mixed with metal oxide, and obtained in the surface of mixture injection silica.
Preferably, the silicon that the quality of titanyl sulfate and carbon material obtain after mixing with silica in titanyl sulfate solution
The mass ratio of carbon composite is 0.8-1.6；
Preferably, ammonium ion and the molar ratio of titanyl sulfate are greater than 2 in ammonia spirit；
Preferably, the mass ratio of lead salt and titanium Si-C composite material is 3.75-6.25 in lead salt solution；
Preferably, the molar ratio of acid group and lead salt is greater than 1 in acid solution.
Further, carbon material includes crystalline flake graphite, expansible graphite, aquadag, acetylene black, superconduction carbon black, centre
At least one of phase carbosphere, spherical graphite, capacitor stage active carbon, carbon fiber, carbon nanotube and graphene.
Preferably, lead titanium Si-C composite material specific surface area is greater than or is equal to 2000m2/ g, particle size range 200-300
Mesh.
Preferably, lead sulfate-carbon-based material combination electrode material and metal oxide are with the mixing of 100:1 ratio, by dioxy
SiClx is injected in the surface of mixture to form uniform micron order little particle, metal oxide include indium oxide, niobium oxide and
At least one of bismuth oxide.
According to second aspect, a kind of preparation method of lead titanium Si-C composite material is provided in a kind of embodiment, step is extremely
Include: less
S1, carbon material is mixed with silica, obtains Si-C composite material；
S2, titanyl sulfate solution is added into Si-C composite material, is calcined under a nitrogen atmosphere after being washed with ammonia spirit
Obtain titanium Si-C composite material；
S3, lead salt solution is added into titanium Si-C composite material, with being dried to obtain lead sulfate-carbon substrate after acid solution wash
Expect combination electrode material；
S4, the lead sulfate-carbon-based material combination electrode material is mixed with metal oxide, after mixing and in mixture
Silica is sprayed on surface, obtains lead titanium Si-C composite material.
Preferably, the specific steps of S2 include: that it is molten that titanyl sulfate is added into Si-C composite material under ultrasonic wave stirring
Liquid, ultrasonic vibration obtain titanium silicon-carbon mixed liquor after a certain period of time, and ammonia spirit, stirred diafiltration are added dropwise into titanium silicon-carbon mixed liquor
Titanium silicon-carbon solid is obtained after washing, and titanium silicon-carbon solid is dried in vacuo under the conditions of certain temperature, and in certain temperature and nitrogen
Under the conditions of calcine a period of time, obtain titanium Si-C composite material；
Preferably, the specific steps of S3 include: that lead salt solution is added to titanium Si-C composite material under ultrasonic wave stirring
In, ultrasonic vibration obtains lead titanium silicon-carbon mixed liquor after a certain period of time, acid solution is added dropwise while stirring into lead titanium silicon-carbon mixed liquor,
Continue stirring after a certain period of time, lead titanium silicon-carbon solid is obtained by filtration, solid is dried at a certain temperature, obtains lead sulfate-carbon
Sill combination electrode material；
Preferably, the specific steps of S4 include: to mix lead sulfate-carbon-based material combination electrode material with metal oxide
Mixture is formed, the surface that silica is injected in mixture is formed to uniform micron order little particle, it is multiple to obtain lead titanium silicon-carbon
Condensation material.
Preferably, preparation method specific steps include:
80-90 parts of carbon materials are mixed with 10-20 parts of silica, obtain Si-C composite material；
Under 25-70 DEG C, the ultrasonic wave stirring that frequency is 10-30khz, it is molten that titanyl sulfate is added into Si-C composite material
Liquid obtains titanium silicon-carbon mixed liquor after ultrasonic vibration 30-60min, ammonia spirit, agitation and filtration is added dropwise into lead titanium silicon-carbon mixed liquor
Titanium silicon-carbon solid is obtained after washing, titanium silicon-carbon solid is dried in vacuo at 60 DEG C, and one section is calcined under 400 DEG C of condition of nitrogen gas
Time obtains titanium Si-C composite material；
Under 25-70 DEG C, the ultrasonic wave stirring that frequency is 10-30khz, lead salt solution is added to titanium Si-C composite material
In, lead titanium silicon-carbon mixed liquor is obtained after ultrasonic vibration 30-60min, and acid solution is added dropwise while stirring into lead titanium silicon-carbon mixed liquor,
Continue after stirring 30-60min, lead titanium silicon-carbon solid is obtained by filtration, by lead titanium silicon-carbon solid at 40-80 DEG C, dry 3-6h is obtained
To lead sulfate-carbon-based material combination electrode material；
Lead sulfate-carbon-based material combination electrode material and metal oxide are mixed to form mixture with 100:1 ratio, it will
The surface that silica is injected in mixture forms uniform micron order little particle, obtains lead titanium Si-C composite material；
Wherein, the mass ratio of titanyl sulfate solution and Si-C composite material is 0.8-1.6；
Ammonium ion and the molar ratio of titanyl sulfate are greater than 2 in ammonia spirit；
The mass ratio of lead salt and titanium Si-C composite material is 3.75-6.25 in lead salt solution；
The molar ratio of acid group and lead salt is greater than 1 in acid solution.
Preferably, carbon material includes crystalline flake graphite, expansible graphite, aquadag, acetylene black, superconduction carbon black, interphase
At least one of carbosphere, spherical graphite, capacitor stage active carbon, carbon fiber, carbon nanotube and graphene.
Preferably, carbon material includes 20-30 parts of spherical graphites, 15-40 parts of acetylene blacks, 15-50 parts of active carbons and 15-40 parts
Carbon fiber.
According to the lead titanium Si-C composite material of above-described embodiment, compared with prior art, the advantage is that:
Using carbon material, silica, titanyl sulfate and lead salt solution, as raw material, compound to obtain lead titanium silicon-carbon compound
Material is had the advantage that using the prepared battery of lead titanium Si-C composite material
Lead titanium Si-C composite material binding force enhancing after in conjunction with lead, makes it keep some strength in charge and discharge process,
It will not loosely fall off because of rush of current；
Lead salt can be converted in active lead, lead salt crystalline solid is inhibited to increase and salinization；
After metal oxide is added, its electric conductivity is improved, wherein specific capacitance value reaches 250F/g or more, and specific capacitance mentions
1.5-2 times high, overpotential of hydrogen evolution improves 100mv, therefore is able to suppress cathode and loses hydrogen too early；
In the case where the charging of low range unsaturation, after cycle-index reaches 360 times, battery capacity is compared with initial capacity
100% or more of capacity, charge and discharge ability to accept improve 50% than conventional lead acid battery more in the early stage, which has good
Capacity maintenance rate has good charged recovery charge characteristic；
In the case where the charging of high magnification unsaturation, under the conditions of PSOC, 10% electric discharge is deep in powerful charging or discharging current
Degree shows good cycle life characteristics, reaches 16000 times, improves the charge acceptance of battery.
Detailed description of the invention
Fig. 1 is a kind of scanning electron microscope schematic diagram of embodiment of lead titanium Si-C composite material in the present invention.
Specific embodiment
Below by specific embodiment combination attached drawing, invention is further described in detail.In the following embodiments and the accompanying drawings
In, many datail descriptions are in order to enable the application can be better understood.However, those skilled in the art can be without lifting an eyebrow
Recognize, part of feature is dispensed in varied situations, or can be substituted by other materials, method.
In some cases, the relevant some operations of the application there is no display in the description or describe, this is in order to avoid this
The core of application is flooded by excessive description, and to those skilled in the art, these correlations behaviour is described in detail
Be not necessary, they according to the general technology knowledge of description and this field in specification can be complete decorrelation
Operation.
It is formed respectively in addition, feature described in this description, operation or feature can combine in any suitable way
Kind embodiment.Meanwhile each step in method description or movement can also can be aobvious and easy according to those skilled in the art institute
The mode carry out sequence exchange or adjustment seen.Therefore, the various sequences in the description and the appended drawings are intended merely to clearly describe a certain
A embodiment is not meant to be necessary sequence, and wherein some sequentially must comply with unless otherwise indicated.
Referring to Figure 1, in embodiments of the present invention, a kind of lead titanium Si-C composite material is provided, the lead titanium silicon-carbon is compound
Material specific surface area is greater than or equal to 2000m2/ g, such as: 2000m2/ g, 2200m2/ g, 2500m2/ g, 2700m2/ g, 3000,
4000m2/ g, 5000m2/ g or 6000m2/ g etc., particle size range are 200-300 mesh, such as: 200 mesh, 220 mesh, 250 mesh, 270
Mesh, 290 mesh or 300 mesh etc..Specific capacitance is generally 265, such as 250, and 255,260,265,270,275 etc..
The lead titanium Si-C composite material is that sulfuric acid oxygen is added after being mixed by 80-90 parts of carbon materials with 10-20 parts of silica
Titanium solution, the titanium Si-C composite material calcined under a nitrogen atmosphere after being washed with ammonia spirit add lead salt solution, use
Acid solution wash is dried to obtain lead sulfate-carbon-based material combination electrode material, lead sulfate-carbon-based material combination electrode material and gold
After belonging to oxide with the mixing of 100:1 ratio, silica is injected in lead sulfate-carbon-based material combination electrode material surface and is obtained
's.Uniform micron order little particle, metal oxide can be formed on the surface of lead titanium Si-C composite material after injection silica
Including at least one of indium oxide, niobium oxide and bismuth oxide.
Wherein the mass ratio of carbon material and silica may is that 8.0:2.0,8.2:1.8,8.5:1.5,8.8:1.2,
Or 9.0:1.0 etc..
The silicon-carbon that wherein quality of titanyl sulfate and carbon material obtain after mixing with silica in titanyl sulfate solution is multiple
The mass ratio of condensation material is 0.8-1.6, and specific value may is that 0.8,1.0,1.2,1.4 or 1.6；
Ammonium ion and the molar ratio of titanyl sulfate are greater than 2 in ammonia spirit, may is that 2,3 or 4；
The mass ratio of lead salt and titanium Si-C composite material is 3.75-6.25 in lead salt solution, and specific value may is that
3.75,3.8,4.0,4.2,4.5,4.8,5.0,5.5,6.0,6.25 etc.；
The molar ratio of acid group and lead salt is greater than 1 in acid solution, can be 1.0,1.1,1.2,1.3,1.4,1.5,2.0,
2.5,3.0 etc..
Wherein, carbon material includes crystalline flake graphite, expansible graphite, aquadag, acetylene black, superconduction carbon black, mesocarbon
At least one of microballoon, spherical graphite, capacitor stage active carbon, carbon fiber (VGCF), carbon nanotube and graphene.Wherein one
It is by 20-30 parts of spherical graphites, 15-40 parts of acetylene blacks, 15-50 parts of active carbons and 15-40 parts that the preferred scheme of kind, which is carbon material,
What carbon fiber was mixed to get.Preferably, in a kind of specific embodiment mode, carbon material be by 20-30 parts of spherical graphites,
What 20-30 parts of acetylene blacks, 20-30 parts of active carbons and 20-30 parts of carbon fibers were mixed to get；In another specific embodiment mode
In, carbon material is mixed by 20-30 parts of spherical graphites, 30-40 parts of acetylene blacks, 15-25 parts of active carbons and 30-40 parts of carbon fibers
It arrives；In another specific embodiment mode, carbon material is by 20-30 parts of spherical graphites, 15-25 parts of acetylene blacks, 40-50
What part active carbon and 15-25 parts of carbon fibers were mixed to get.
As shown in Figure 1, each component material is tightly combined each other and divides in lead titanium Si-C composite material provided by the invention
Cloth is uniform, and the low range unsaturation charge and discharge mode of solar energy and wind energy and the frequency of smart grid are not only met on partial size
The requirement of numerous fast charging and discharging mode, and when lead titanium Si-C composite material makes an addition in cathode, can also reinforce intensity and enhancing
Binding force.
A kind of preparation method of lead titanium Si-C composite material is also provided in the embodiment of the present invention, step includes at least:
S1, Si-C composite material is prepared.80-90 parts of carbon materials are uniformly mixed into 2h with 10-20 parts of silica, obtain silicon
Carbon composite.Wherein carbon material includes crystalline flake graphite, expansible graphite, aquadag, acetylene black, superconduction carbon black, interphase
At least one of carbosphere, spherical graphite, capacitor stage active carbon, carbon fiber, carbon nanotube and graphene.One of which tool
Carbon material is by 20-30 parts of spherical graphites, 15-40 parts of acetylene blacks, 15-50 parts of active carbons and 15-40 parts of carbon fibers in body embodiment
What dimension was mixed to get.In second of specific embodiment, carbon material be by 20-30 parts of spherical graphites, 20-30 parts of acetylene blacks,
What 20-30 parts of active carbons and 20-30 parts of carbon fibers were mixed to get.In the third specific embodiment, carbon material is by 20-30
What part spherical graphite, 30-40 parts of acetylene blacks, 15-25 parts of active carbons and 30-40 parts of carbon fibers were mixed to get.It is specific at the 4th kind
Embodiment side in, carbon material is by 20-30 parts of spherical graphites, 15-25 parts of acetylene blacks, 40-50 parts of active carbons and 15-25 parts of carbon
What fiber was mixed to get.
After mixing the grain diameter of Si-C composite material be 50nm~20um, aperture be 2~150nm, Kong Rongwei 0.1~
1.5cm3/ g, specific surface area are 30~300m2/g.Mixed silica is porous silicon matrix, and carbon material is straight with nano-form
It connects and is grown on porous silicon matrix, after carbon material one or both ends are in conjunction with porous silicon matrix, carbon material is coated, and forms silicon
Carbon composite.
S2, titanium Si-C composite material is prepared.It is past to contain silicon under 25-70 DEG C, the ultrasonic wave stirring that frequency is 10-30khz
Titanyl sulfate solution is added in the suspension of carbon composite, titanium silicon-carbon mixed liquor is obtained after ultrasonic vibration 30-60min.It is stirring
Mix it is lower ammonia spirit is added dropwise into titanium silicon-carbon mixed liquor, 30-60min is stirred after dripping, and titanium silicon-carbon is obtained after filtration washing
Solid.Titanium silicon-carbon solid is dried in vacuo 8h at 60 DEG C, and calcines 4h under 400 DEG C of condition of nitrogen gas, it is compound to obtain titanium silicon-carbon
Material.Wherein the mass ratio of titanyl sulfate solution and Si-C composite material is 0.8-1.6；Ammonium ion and sulfuric acid in ammonia spirit
The molar ratio of oxygen titanium is greater than 2.The load factor of titanium dioxide can reach 20-30% at this time.
S3, lead titanium Si-C composite material is prepared.Under 25-70 DEG C, the ultrasonic wave stirring that frequency is 10-30khz, by lead salt
Solution is added in the suspension containing titanium Si-C composite material, and lead titanium silicon-carbon mixed liquor is obtained after ultrasonic vibration 30-60min.To
Acid solution is added dropwise while stirring in lead titanium silicon-carbon mixed liquor, continues to stir 30-60min after dripping, lead titanium silicon-carbon is obtained by filtration
Solid, by lead titanium silicon-carbon solid at 40-80 DEG C, dry 3-6h obtains lead sulfate-carbon-based material combination electrode material.Wherein
Lead salt solution can be lead acetate or plumbi nitras, and acid solution can be sulfuric acid.Lead salt and titanium Si-C composite material in lead salt solution
Mass ratio be 3.75-6.25.The molar ratio of acid group and lead salt is greater than 1 in acid solution.The load factor of lead salt can reach 40- at this time
50%.
S4, lead sulfate-carbon-based material combination electrode material and metal oxide are mixed to form mixing with 100:1 ratio
The surface that silica is injected in mixture is formed uniform micron order little particle by object, to obtain lead titanium silicon-carbon composite wood
Material.Wherein metal oxide can be at least one of indium oxide, niobium oxide and bismuth oxide.
Embodiment one:
Present embodiment discloses a kind of preparation method of lead titanium Si-C composite material, specific steps include:
S10, Si-C composite material is prepared.Carbon material is mixed according to following mass ratio:
Spherical graphite is 25%, and phosphorus content is greater than 99%, and granularity D50 is 15-20um, specific surface area 4-6.5m2/g；
Acetylene black is 25%, average grain diameter 25-30nm, specific surface area 250-300m2/g；
Active carbon is 25%, aperture 2-2.2nm, Kong Rongwei 1-1.2cm3/ g, specific surface area 2000m2/ g or more,
Inorganic mass specific capacitance is 280F/g；
Carbon fiber is 25%, specific surface area 15-20m2/ g, length 5-8um, diameter 150nm, electrical conductivity are
1*10-4Ω/cm；
Mixing material is obtained after uniform stirring, silica is added into mixing material, and wherein the quality of silica accounts for
The 15% of mixing material.2h is continuesd to mix, Si-C composite material is formed.
S20, titanium Si-C composite material is prepared.It is under 50 DEG C, the ultrasonic wave stirring that frequency is 20khz, titanyl sulfate is molten
Liquid is added in the suspension containing silicon-carbon based composites, and ultrasonic vibration 45min obtains titanium silicon-carbon mixed liquor.Under stiring to titanium
Ammonia spirit is added dropwise in silicon-carbon mixed liquor, after being added dropwise, continues to stir 45min, filtration washing obtains titanium silicon-carbon solid.By titanium
Silicon-carbon solid is placed at 60 DEG C and is dried in vacuo 8h, calcines 4h under 400 DEG C of condition of nitrogen gas, obtains titanium Si-C composite material.Wherein
The mass ratio of titanyl sulfate solution and Si-C composite material is 1.2；The molar ratio of ammonium ion and titanyl sulfate in ammonia spirit
Equal to 2.
S30, lead titanium Si-C composite material is prepared.It is under 55 DEG C, the ultrasonic wave stirring that frequency is 20khz, lead acetate is molten
Liquid is added in the suspension containing titanium Si-C composite material, and lead titanium silicon-carbon mixed liquor is obtained after ultrasonic vibration 45min.To lead titanium silicon
Sulfuric acid solution is added dropwise while stirring in carbon mixed liquor, continues to stir 45min after being added dropwise, lead titanium silicon-carbon solid is obtained by filtration,
By lead titanium silicon-carbon solid at 60 DEG C, dry 4.5h obtains lead sulfate-carbon-based material combination electrode material.Wherein lead salt solution
It can be lead acetate or plumbi nitras, acid solution can be sulfuric acid.The mass ratio of lead salt and titanium Si-C composite material in lead salt solution
It is 4.The molar ratio of acid group and lead salt is greater than 2 in acid solution.
S40, by lead sulfate-carbon-based material combination electrode material, the metal oxide that is formed with indium oxide and niobium oxide with
100:1 ratio is mixed to form mixture, and the surface that silica is injected in mixture is formed to uniform micron order little particle, from
And obtain lead titanium Si-C composite material.
Embodiment two:
In preparation method disclosed in the present embodiment, it is the step of preparing Si-C composite material with one difference of embodiment,
Remaining specific steps are identical.
S11, Si-C composite material is prepared.Carbon material is mixed according to following mass ratio:
Spherical graphite is 25%, and phosphorus content is greater than 99%, and granularity D50 is 15-20um, specific surface area 4-6.5m2/g；
Acetylene black is 35%, average grain diameter 25-30nm, specific surface area 250-300m2/g；
Active carbon is 20%, aperture 2-2.2nm, Kong Rongwei 1-1.2cm3/ g, specific surface area 2000m2/ g or more,
Inorganic mass specific capacitance is 280F/g；
Carbon fiber is 35%, specific surface area 15-20m2/ g, length 5-8um, diameter 150nm, electrical conductivity are
1*10-4Ω/cm；
Mixing material is obtained after uniform stirring, silica is added into mixing material, and wherein the quality of silica accounts for
The 10% of mixing material.2h is continuesd to mix, Si-C composite material is formed.
Embodiment three:
In preparation method disclosed in the present embodiment, it is the step of preparing Si-C composite material with one difference of embodiment,
Remaining specific steps are identical.
S111, Si-C composite material is prepared.Carbon material is mixed according to following mass ratio:
Spherical graphite is 25%, and phosphorus content is greater than 99%, and granularity D50 is 15-20um, specific surface area 4-6.5m2/g；
Acetylene black is 20%, average grain diameter 25-30nm, specific surface area 250-300m2/g；
Active carbon is 45%, aperture 2-2.2nm, Kong Rongwei 1-1.2cm3/ g, specific surface area 2000m2/ g or more,
Inorganic mass specific capacitance is 280F/g；
Carbon fiber is 20%, specific surface area 15-20m2/ g, length 5-8um, diameter 150nm, electrical conductivity are
1*10-4Ω/cm；
Mixing material is obtained after uniform stirring, silica is added into mixing material, and wherein the quality of silica accounts for
The 20% of mixing material.2h is continuesd to mix, Si-C composite material is formed.
Lead titanium silicon-carbon obtained by embodiment one, two, three and common carbon material are mixed with binder respectively, used is viscous
Knot agent is polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF), Sodium Polyacrylate (PAANA), sodium carboxymethylcellulose
(CMC), at least one of butadiene-styrene rubber (SBR), LA132, LA133, neoprene.It is preferred that PTFE, SBR and/or LA132.With
Spraying method is applied to 2cm2Pure stereotype two sides, obtain clad plate.Add up to coating 0.5g binder at this time.In above-mentioned coating
The two sides of plate are superimposed two lead dioxide electrodes of the same area and are used as to pole plate, and are wrapped up with AGM diaphragm, form pole group, erect
Directly organic glass is put into do in transparent electrolytic bath.The pressure of pole group is adjusted with pressure regulation piece to 20Kpa, injecting specific gravity is 1.3
In sulfuric acid electrolyte, the battery of four different materials is respectively obtained, is denoted as battery one, battery two, battery three and control electricity
Pond.Its test content is as follows:
One, hydrogen-evolution overpotential compares
When carrying out hydrogen-evolution overpotential research, four battery chem workstations are carried out cyclic voltammetry scan, setting
Scanning speed is 10mv/s, and potential range is -1.6V~+1Vvs, Hg/HgSO4.By the method to the four poles group studied
10 times repeatedly scan round is carried out, the take-off potential and record that the 10th circulating hydrogen of measurement generates.
Two, specific capacitance value
It is connected respectively on charge and discharge instrument after the measurement of above-mentioned hydrogen-evolution overpotential, then electrode lamination, is put using constant current
The form of electricity respectively obtains the capacitance of three kinds of C-base composte materials and common carbon material with 100mA charge and discharge.Hydrogen-evolution overpotential and
Specific capacitance value test result is referring to table 1:
1 hydrogen-evolution overpotential of table and specific capacitance value
It is compared by the data to table 1, it can be seen that using the liberation of hydrogen of the battery one to three of lead titanium Si-C composite material
Current potential is at least up to -1.49Hg/HgSO4, higher than-the 1.40Hg/HgSO of control cell4, the specific capacitance value of battery one to three is high
In 200F/g, hence it is evident that it is higher than control cell, illustrate overpotential of hydrogen evolution and ratio that battery can be improved using lead titanium Si-C composite material
Capacitance.
Three, (PSOC) charge-discharge cycle life test under undersaturated condition
(1), the 10HR capacity comparison test result of LR-PSOC (low range part) charge and discharge circulation life test is referring to table
2:
2 10HR capacity ratio of table (% is to initial stage)
| Cycle-index | 90 times | 180 times | 270 times | 360 times |
| Battery one | 101 | 103 | 103 | 104 |
| Battery two | 101 | 103 | 104 | 105 |
| Battery three | 101 | 102 | 102 | 103 |
| Control cell | 97 | 96 | 94 | 92 |
It is compared by the data to table 2, it can be seen that using the battery one to three of lead titanium Si-C composite material low
In the case that multiplying power unsaturation charges, battery capacity is in the fair state that rises to compared with initial capacity, and uses common
The capacity of the control cell of material is constantly in attenuation state.Restore charging after 360 circulations, one to three capacity of battery is still first
100% or more of phase capacity, and common standard battery maintains 92%, illustrates have using the battery of lead titanium Si-C composite material
There is good capacity sustainment rate, there is good charged recovery charge characteristic.
(2), the result of HRPSOC (high magnification part) charge and discharge circulation life test is referring to table 3, HRPSOC charge and discharge end
The test result of phase voltage is referring to table 4:
3 HR-PSOC capacity maintenance rate of table (% is to initial stage)
| Cycle-index | 2000 times | 4000 times | 6000 times | 8000 times | 10000 times | 12000 times |
| Battery one | 90 | 89 | 85 | 84 | 83 | 81 |
| Battery two | 94 | 92 | 90 | 89 | 85 | 84 |
| Battery three | 91 | 89 | 86 | 84 | 82 | 80 |
| Control cell | 85 | 79 | 71 | 65 | 56 | 50 |
It is compared by the data to table 3, it can be seen that although battery one to three and control cell are in high magnification insatiable hunger
With battery capacity in the case where charging compared with initial capacity all in the state of decaying.But it is compound using lead titanium silicon-carbon
The attenuation degree of the prepared battery one to three of material still reaches 80% or more of initial capacity, and the capacity compared with control cell declines
Subtract degree and want low, illustrates to use the prepared cell decay degree of lead titanium Si-C composite material small, service life is longer.
4 HR-PSOC charge and discharge latter stage voltage of table
It is compared by the data to table 4, it can be seen that using the battery one to three of lead titanium Si-C composite material in height
Battery latter stage of charging voltage is fluctuated in 2.4V or less in the case that multiplying power unsaturation charges, however pair obtained using common material
It is fluctuated according to the latter stage of charging voltage of battery in 2.45V or so, the battery in the case where high magnification unsaturation charges of battery one to three
Latter stage voltage discharge compared with the latter stage of charging voltage of control cell, although unobvious in the early stage, with cycle-index
It increases, electric discharge latter stage voltage difference is also increasing, and the difference of the electric discharge latter stage voltage passage in cyclic test does not have latter stage of charging
Change before reaching final voltage frequently, it is the good reason of charge acceptance that battery charging voltage, which is stablized,.On the whole,
Lead titanium Si-C composite material function admirable.
By the capacity maintenance rate of 1C1A at 80%, battery cycle life is about that tradition is stored with capacity long-life circulation with lead
2 times of battery.
Therefore, lead titanium silicon-carbon is obtained as raw material are compound using carbon material, silica, titanyl sulfate and lead salt solution
Composite material is simultaneously applied in battery, when so that battery improving cycle life, charge and discharge ability to accept ratio and shortens charging
Between.Specific capacitance and overpotential of hydrogen evolution are improved simultaneously.It is experimentally confirmed, battery is under the conditions of PSOC, powerful charging or discharging current
In 10% depth of discharge show good cycle life characteristics, reach 16000 times；Battery is powerful under the conditions of PSOC
Charging and discharging currents also show good cycle life characteristics.In addition, inhibiting battery negative by electric conductivity and the binding force of lead plaster
The problems such as sulfation of pole, active matter fall off, cathode too early liberation of hydrogen.
The above advantage is applied to lead titanium Si-C composite material of the invention in battery, can be improved battery PSOC circulation
Service life enhances high rate performance and restores charge characteristic, meets solar energy, the power generation of wind energy renewable resource and smart grid to storage
The requirement of energy battery.
Use above specific case is illustrated the present invention, is merely used to help understand the present invention, not to limit
The system present invention.For those skilled in the art, according to the thought of the present invention, can also make several simple
It deduces, deform or replaces.
Claims (15)
1. a kind of lead titanium Si-C composite material, which is characterized in that the lead titanium Si-C composite material is by carbon material and titanium dioxide
After silicon mixing, titanyl sulfate solution, the titanium silicon-carbon composite wood calcined under a nitrogen atmosphere after being washed with ammonia spirit is added
Material, adds lead salt solution, with acid solution wash, the lead sulfate-carbon-based material combination electrode material and metal obtained after dry
Oxide mixing, and obtained in the surface of mixture injection silica, the metal oxide includes indium oxide, niobium oxide
At least one of with bismuth oxide.
2. lead titanium Si-C composite material as described in claim 1, which is characterized in that titanyl sulfate in the titanyl sulfate solution
Quality and the carbon material mixed with the silica after the obtained mass ratio of Si-C composite material be 0.8-1.6.
3. lead titanium Si-C composite material as described in claim 1, which is characterized in that ammonium ion and institute in the ammonia spirit
The molar ratio for stating titanyl sulfate is greater than 2.
4. lead titanium Si-C composite material as described in claim 1, which is characterized in that lead salt and the titanium in the lead salt solution
The mass ratio of Si-C composite material is 3.75-6.25.
5. lead titanium Si-C composite material as described in claim 1, which is characterized in that acid group and the lead salt in the acid solution
Molar ratio be greater than 1.
6. lead titanium Si-C composite material as described in claim 1, which is characterized in that the carbon material includes crystalline flake graphite, can
Expanded graphite, aquadag, acetylene black, superconduction carbon black, carbonaceous mesophase spherules, spherical graphite, capacitor stage active carbon, carbon fiber,
At least one of carbon nanotube and graphene.
7. such as lead titanium Si-C composite material described in any one of claims 1 to 6, which is characterized in that the lead titanium silicon-carbon is multiple
Condensation material specific surface area is greater than or is equal to 2000m2/ g, particle size range are 200-300 mesh.
8. a kind of lead titanium Si-C composite material as described in claim 1, which is characterized in that the lead sulfate-carbon-based material is multiple
Silica is injected in the surface of the mixture with the mixing of 100:1 ratio to be formed by composite electrode material and metal oxide
Uniform micron order little particle.
9. a kind of preparation method of lead titanium Si-C composite material, which is characterized in that its step includes at least:
S1, carbon material is mixed with silica, obtains Si-C composite material；
Titanyl sulfate solution is added in S2, Xiang Suoshu Si-C composite material, is calcined under a nitrogen atmosphere after being washed with ammonia spirit
Obtain titanium Si-C composite material；
S3, lead salt solution is added into the titanium Si-C composite material, with being dried to obtain lead sulfate-carbon substrate after acid solution wash
Expect combination electrode material；
S4, the lead sulfate-carbon-based material combination electrode material is mixed with metal oxide, after mixing and on mixture surface
Silica is sprayed, obtains lead titanium Si-C composite material, the metal oxide includes in indium oxide, niobium oxide and bismuth oxide
It is at least one.
10. the preparation method of lead titanium Si-C composite material as claimed in claim 9, which is characterized in that the specific step of the S2
Suddenly include:
Under ultrasonic wave stirring, titanyl sulfate solution is added into the Si-C composite material, titanium silicon-carbon is obtained after ultrasonic vibration
Ammonia spirit is added dropwise in Xiang Suoshu mixed liquor, obtains titanium silicon-carbon solid after agitation and filtration washing, the titanium silicon-carbon is consolidated for mixed liquor
Body vacuum drying, and calcining a period of time under a nitrogen atmosphere, obtain titanium Si-C composite material.
11. the preparation method of lead titanium Si-C composite material as claimed in claim 9, which is characterized in that the specific step of the S3
Suddenly include:
Under ultrasonic wave stirring, lead salt solution is added in titanium Si-C composite material, the mixing of lead titanium silicon-carbon is obtained after ultrasonic vibration
Acid solution is added dropwise into mixed liquor while stirring for liquid, and after continuing stirring, lead titanium silicon-carbon solid is obtained by filtration, and solid is dry, obtains
To lead sulfate-carbon-based material combination electrode material.
12. the preparation method of lead titanium Si-C composite material as claimed in claim 9, which is characterized in that the specific step of the S4
It suddenly include: that the lead sulfate-carbon-based material combination electrode material and metal oxide are mixed to form mixture, by silica
The surface for being injected in the mixture forms uniform micron order little particle, obtains lead titanium Si-C composite material.
13. the preparation method of lead titanium Si-C composite material as claimed in claim 9, which is characterized in that its specific steps includes:
80-90 parts of carbon materials are mixed with 10-20 parts of silica, obtain Si-C composite material；
Under 25-70 DEG C, the ultrasonic wave stirring that frequency is 10-30khz, it is molten that titanyl sulfate is added into the Si-C composite material
Liquid obtains titanium silicon-carbon mixed liquor after ultrasonic vibration 30-60min；Ammonia spirit, agitation and filtration washing are added dropwise into the mixed liquor
After obtain titanium silicon-carbon solid, the titanium silicon-carbon solid is dried in vacuo at 60 DEG C, and under 400 DEG C of condition of nitrogen gas calcine one section
Time obtains titanium Si-C composite material；
Under 25-70 DEG C, the ultrasonic wave stirring that frequency is 10-30khz, lead salt solution is added in titanium Si-C composite material, is surpassed
Acoustic shock obtains lead titanium silicon-carbon mixed liquor after swinging 30-60min, and acid solution is added dropwise while stirring into mixed liquor, continues to stir 30-
After 60min, lead titanium silicon-carbon solid is obtained by filtration, by solid at 40-80 DEG C, it is multiple to obtain lead sulfate-carbon-based material by dry 3-6h
Composite electrode material；
The lead sulfate-carbon-based material combination electrode material and metal oxide are mixed to form mixture with 100:1 ratio, it will
The surface that silica is injected in the mixture forms uniform micron order little particle, obtains lead titanium Si-C composite material；
Wherein, the mass ratio of the titanyl sulfate solution and the Si-C composite material is 0.8-1.6；
Ammonium ion and the molar ratio of the titanyl sulfate are greater than 2 in the ammonia spirit；
The mass ratio of lead salt and the titanium Si-C composite material is 3.75-6.25 in the lead salt solution；
The molar ratio of acid group and the lead salt is greater than 1 in the acid solution.
14. the preparation method of the lead titanium Si-C composite material as described in any in claim 9 to 13, which is characterized in that described
Carbon material include crystalline flake graphite, expansible graphite, aquadag, acetylene black, superconduction carbon black, carbonaceous mesophase spherules, spherical graphite,
At least one of capacitor stage active carbon, carbon fiber, carbon nanotube and graphene.
15. the preparation method of lead titanium Si-C composite material as claimed in claim 14, which is characterized in that the carbon material includes
20-30 parts of spherical graphites, 15-40 parts of acetylene blacks, 15-50 parts of active carbons and 15-40 parts of carbon fibers.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4381250A (en) * | 1980-12-03 | 1983-04-26 | Allied Corporation | Curing of tetrabasic lead pasted battery electrodes |
| CN102306784A (en) * | 2011-06-29 | 2012-01-04 | 哈尔滨工业大学 | Modified activated carbon with high hydrogen evolution potential and preparation method thereof as well as lead-acid battery negative lead paste containing modified activated carbon |
| CN103043659A (en) * | 2012-12-17 | 2013-04-17 | 湖南丰日电源电气股份有限公司 | Preparation method for modified actived carbons |
| CN104393250A (en) * | 2014-10-22 | 2015-03-04 | 南京航空航天大学 | Preparation method for lead-carbon composite material of lead acid battery and composite negative plate |
| CN104900851A (en) * | 2015-06-24 | 2015-09-09 | 湖北骆驼蓄电池研究院有限公司 | Cathode for lead-carbon batteries, production method of cathode and battery made with cathode |
-
2017
- 2017-04-13 CN CN201710240199.9A patent/CN106941166B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4381250A (en) * | 1980-12-03 | 1983-04-26 | Allied Corporation | Curing of tetrabasic lead pasted battery electrodes |
| CN102306784A (en) * | 2011-06-29 | 2012-01-04 | 哈尔滨工业大学 | Modified activated carbon with high hydrogen evolution potential and preparation method thereof as well as lead-acid battery negative lead paste containing modified activated carbon |
| CN103043659A (en) * | 2012-12-17 | 2013-04-17 | 湖南丰日电源电气股份有限公司 | Preparation method for modified actived carbons |
| CN104393250A (en) * | 2014-10-22 | 2015-03-04 | 南京航空航天大学 | Preparation method for lead-carbon composite material of lead acid battery and composite negative plate |
| CN104900851A (en) * | 2015-06-24 | 2015-09-09 | 湖北骆驼蓄电池研究院有限公司 | Cathode for lead-carbon batteries, production method of cathode and battery made with cathode |
Non-Patent Citations (1)
| Title |
|---|
| "三种负极材料添加对铅酸电池循环寿命影响";于占河 等;《电源技术》;20170120;第41卷(第1期);第75-77页 |
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