CN108122683A - A kind of preparation of interior mixed interior and mixed type lead carbon battery and cathode - Google Patents
A kind of preparation of interior mixed interior and mixed type lead carbon battery and cathode Download PDFInfo
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- CN108122683A CN108122683A CN201611061063.3A CN201611061063A CN108122683A CN 108122683 A CN108122683 A CN 108122683A CN 201611061063 A CN201611061063 A CN 201611061063A CN 108122683 A CN108122683 A CN 108122683A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 228
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 173
- 238000002360 preparation method Methods 0.000 title claims description 28
- 239000002253 acid Substances 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 239000011505 plaster Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 30
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 26
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 16
- 238000007711 solidification Methods 0.000 claims description 16
- 230000008023 solidification Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000005192 partition Methods 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 239000003990 capacitor Substances 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 14
- 239000004743 Polypropylene Substances 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 13
- 239000006258 conductive agent Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 239000011149 active material Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 230000002146 bilateral effect Effects 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229920002972 Acrylic fiber Polymers 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003610 charcoal Substances 0.000 claims description 5
- 239000004021 humic acid Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002245 particle Substances 0.000 claims 2
- 239000002033 PVDF binder Substances 0.000 claims 1
- 239000006230 acetylene black Substances 0.000 claims 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 28
- 238000012360 testing method Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000013019 agitation Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000006071 cream Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 235000013399 edible fruits Nutrition 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 230000019635 sulfation Effects 0.000 description 4
- 238000005670 sulfation reaction Methods 0.000 description 4
- 229910052924 anglesite Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- 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
- H01M16/003—Structural combinations of different types of electrochemical generators of fuel cells with other electrochemical devices, e.g. capacitors, electrolysers
-
- 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
-
- 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
-
- 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
- H01M4/21—Drying of pasted electrodes
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to interior and mixed type lead carbon battery is mixed in one kind.The structure feature of the battery is inside and substitutes lead-acid battery cathode with interior mixed type lead carbon battery cathode in type lead carbon superbattery.Since charge acceptance, deep discharge ability and the charge and discharge cycles stability of interior mixed type lead carbon battery cathode are significantly larger than lead-acid battery cathode, it is introduced into interior and type lead carbon battery, is beneficial to the raising of cell output and stability.Using simultaneously mixed type lead carbon superbattery has different performances in being mixed in different distribution form cathode, different application demands disclosure satisfy that.Interior mixed interior and mixed type lead carbon battery discharge and recharge reaction invertibity, charge and discharge circulation life and charge acceptance are significantly better than traditional lead acid batteries.
Description
Technical field
The invention belongs to lead carbon battery technical fields, and in particular to a kind of ultracapacitor is combined with interior mixed type lead carbon battery
It is interior simultaneously/interior dark mould assembly 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.
According to the layout type of electrode, lead carbon battery can be divided into interior mixing and two types.
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.
Interior and type lead carbon superbattery is by Asymmetric Supercapacitor and lead-acid battery using the unification of both interior parallel way.
As a kind of new superbattery, interior and type lead carbon battery be by the fusion of both lead-acid battery and ultracapacitor technology,
It is a kind of not only difunctional energy-storage battery with capacitance characteristic but also with battery behavior.Interior and type lead carbon battery is except with super
The advantages of capacitance high power density, the also advantage with lead-acid battery high-energy density.
Inside and in type lead carbon superbattery, with interior mixed type lead carbon battery cathode and electrode of super capacitor parallel technology side
The case substitution lead-acid battery cathode technical solution in parallel with electrode of super capacitor, can be born efficiently against due to lead-acid battery
The attenuation of battery performance caused by the sulfation of pole further improves interior and type lead carbon superbattery cycle life.
As the carbon material of interior mixed type lead carbon battery cathode additive agent, in addition to needing that there is high specific surface area, also
With certain electron conduction.Big surface area can be precipitated for sulphate crystal and provide active sites, and high electronic conduction
Performance enough promotes the reduction reaction of lead sulfate, and the two collective effect can slow down the sulfation of cathode, further improve battery
Charge acceptance.The advantages of modified activated carbon is with high-ratio surface knot and high electron conduction is more satisfactory interior
Mixed type lead carbon battery cathode additive agent.
The content of the invention
In order to solve the above technical problems, the present invention provides a kind of interior mixed interior and mixed type lead carbon superbattery electrode structure
Layout, preparation process and battery encapsulation method.
To achieve the above object, the specific technical solution that the present invention uses is as follows：
It is born for interior and type lead carbon superbattery cathode by ultracapacitor activated carbon electrodes and interior mixed type lead carbon battery
Pole (lead-acid battery cathode for mixing a certain amount of carbon material) is formed in parallel.
Two kinds of electrode parallel ways, i.e. electrode structure layout include following four mode：
Mode one：It mixes to use in type lead carbon battery inside and type lead carbon battery negative plate is mixed in activated carbon electrodes piece partial replacement,
Interior and mixed type lead carbon superbattery is mixed in composition.
(1) preparation method of type lead carbon battery cathode version is mixed in, is included the following steps：
1) modified 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 mixed using high shear agitation machine, and the rotating speed of agitating paddle is 10~50000
Rev/min, mixing time is 0.1~500min.Auxiliary material is one or both of barium sulfate, humic acid.Staple fiber for polypropylene,
One or both of acrylic fiber, length are 1~10mm；
2) water and sulfuric acid are added in into the mixture that step 1) obtains, is sufficiently stirred and prepares lead plaster；The density of sulfuric acid is
1.05~1.85g/cm3(25 DEG C), addition account for the 1~30% of mixture quality, and the addition of water accounts for solid 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 for 1~
50h；Drying temperature is 10~200 DEG C, and relative humidity is 0~80%, drying time for 0.1~for 24 hours.
(2) preparation method of super capacitor anode plate, includes the following steps：
1) by activated carbon, conductive agent and binding agent according to mass ratio (50~95):(1~30):(1~20) it is uniformly mixed,
Obtain carbon paste；
2) carbon paste for obtaining step 1) is coated on negative electrode grid, and carbon paste coated weight is by for 0.01~1g/cm2。
3) the activated carbon negative electrode plate for preparing step 2) dry 0.1 at 20~200 DEG C~for 24 hours.
(3) will (1) and (2) prepare in mix type lead carbon battery negative plate and super capacitor anode plate according to a certain percentage with
Lead-acid battery positive plate combo, and it is with partition plate that pole piece is mutually isolated, interior and mixed type lead carbon battery is mixed in structure.As cathode
Interior mixed type lead carbon battery negative plate and super capacitor anode plate quantity ratio by cathode capacitance and battery capacity ratio, two kinds
The painting cream amount of electrode plate determines.Interior mixed interior and mixed type lead carbon battery positive and negative anodes Capacity Ratio is (10~90):(90~10) are born
Extremely middle capacitance is (1~80) with battery capacity ratio:(10~99).
Mode two：Type lead carbon battery cathode lead plaster is mixed in negative electrode grid Partial Mesh in filling, filling is super in remaining grid
Grade electrode for capacitors active material, mix in composition in and mixed type negative plate.Will in preparation mix in and mixed type negative plate with
Lead-acid battery positive plate combo, the two are separated with partition plate, and interior and mixed type lead carbon superbattery is mixed in composition.
(1) preparation method of interior mixed type lead carbon battery cathode portion in interior and mixed type negative plate is mixed in, including walking as follows
Suddenly：
1) modified 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 mixed using high shear agitation machine, and the rotating speed of agitating paddle is 10~50000
Rev/min, mixing time is 0.1~500min.Auxiliary material is one or both of barium sulfate, humic acid.Staple fiber for polypropylene,
One or both of acrylic fiber, length are 1~10mm；
2) water and sulfuric acid are added in into the mixture that step 1) obtains, is sufficiently stirred and prepares lead plaster；The density of sulfuric acid is
1.05~1.85g/cm3(25 DEG C), addition account for the 1~30% of mixture quality, and the addition of water accounts for solid mixture quality
0.5~50%；
3) lead plaster is scratched into the Partial Mesh of negative electrode grid.Active material thickness is 0.1~10mm on raw pole piece.
(2) preparation method of super capacitor anode part in interior and mixed type negative plate is mixed in, is included the following steps：
1) by activated carbon, conductive agent and binding agent according to mass ratio (50~95):(1~30):(1~20) it is uniformly mixed,
Obtain carbon paste；
2) carbon paste for obtaining step 1) is coated on negative electrode grid in remaining grid, carbon paste coated weight by for 0.01~
1g/cm2.Carbon paste coated area is determined with lead plaster coated area ratio by negative battery capacity and capacitance ratio.Capacitance in cathode
Capacity is (1~80) with battery capacity ratio:(10~99).
3) it is cured to be dried to obtain in mixed simultaneously mixed type negative plate.Solidification temperature is 10~100 DEG C, relative humidity for 10~
100%, hardening time is 1~50h；Drying temperature is 10~200 DEG C, and relative humidity is 0~80%, drying time for 0.1~
24h。
(3) simultaneously mixed type negative plate and lead-acid battery positive plate combo, and with partition plate that pole piece is mutually isolated, structure in being mixed in
Build interior mixed interior and mixed type lead carbon battery.
Mode three：Type lead-acid battery cathode plate unilateral or bilateral surface coating electrode of super capacitor is mixed inside, in composition
In mixed and mixed type negative plate, then with lead-acid battery positive plate combo, the two separates with partition plate, mixed in composition in and mix
Type lead carbon superbattery.
(1) preparation method of interior mixed type lead carbon battery cathode portion in interior and mixed type negative plate is mixed in, including walking as follows
Suddenly：
1) modified 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 mixed using high shear agitation machine, and the rotating speed of agitating paddle is 10~50000
Rev/min, mixing time is 0.1~500min.Auxiliary material is one or both of barium sulfate, humic acid.Staple fiber for polypropylene,
One or both of acrylic fiber, length are 1~10mm；
2) water and sulfuric acid are added in into the mixture that step 1) obtains, is sufficiently stirred and prepares lead plaster；The density of sulfuric acid is
1.05~1.85g/cm3(25 DEG C), addition account for the 1~30% of mixture quality, and the addition of water accounts for solid mixture quality
0.5~50%；
3) lead plaster is scratched onto negative electrode grid, it is cured to be dried to obtain lead carbon battery composite negative pole life pole piece；Raw pole piece
Upper active material thickness is 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 for 0.1~for 24 hours.
(2) preparation method of super capacitor anode part in interior and mixed type negative plate is mixed in, is included the following steps：
1) by activated carbon, conductive agent and binding agent according to mass ratio (50~95):(1~30):(1~20) it is uniformly mixed,
Obtain carbon paste；
2) carbon paste for obtaining step 1) is coated to mode two (1) 3) prepare interior mixed type lead carbon battery negative plate unilateral side
Or on double-sided surface, carbon paste coated weight is by for 0.01~1g/cm2.Carbon paste coated weight is by negative battery capacity and capacitance ratio
It determines.Capacitance and battery capacity ratio are (1~80) in cathode:(10~99).
3) the activated carbon negative electrode plate for preparing step 2) dry 0.1 at 20~200 DEG C~for 24 hours.
(3) simultaneously mixed type negative plate and lead-acid battery positive plate combo, and with partition plate that pole piece is mutually isolated, structure in being mixed in
Build interior mixed interior and mixed type lead carbon battery.
Mode four：Type lead carbon battery negative electrode lead is mixed in the coating of ultracapacitor activated carbon electrodes unilateral or bilateral surface
Cream, mix in composition in and mixed type negative plate, then with lead-acid battery positive plate combo, the two is separated with partition plate, in composition
Mixed interior and mixed type lead carbon superbattery.
(1) preparation method of super capacitor anode part in interior and mixed type negative plate is mixed in, is included the following steps：
1) by activated carbon, conductive agent and binding agent according to mass ratio (50~95):(1~30):(1~20) it is uniformly mixed,
Obtain carbon paste；
2) carbon paste is coated on negative plate, carbon paste coated weight is by for 0.01~1g/cm2。
3) the activated carbon negative electrode plate for preparing step 2) dry 0.1 at 20~200 DEG C~for 24 hours.
(2) preparation method of interior mixed type lead carbon battery cathode portion in interior and mixed type negative plate is mixed in, including walking as follows
Suddenly：
1) modified 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 mixed using high shear agitation machine, and the rotating speed of agitating paddle is 10~50000
Rev/min, mixing time is 0.1~500min.Auxiliary material is one or both of barium sulfate, humic acid.Staple fiber for polypropylene,
One or both of acrylic fiber, length are 1~10mm；
2) water and sulfuric acid are added in into the mixture that step 1) obtains, is sufficiently stirred and prepares lead plaster；The density of sulfuric acid is
1.05~1.85g/cm3(25 DEG C), addition account for the 1~30% of mixture quality, and the addition of water accounts for solid mixture quality
0.5~50%；
3) lead plaster is scratched onto the unilateral or bilateral surface of super capacitor anode plate, lead plaster thickness is 0.1~10mm；
Carbon paste coated area is determined with lead plaster coated area ratio by negative battery capacity and capacitance ratio.Capacitance and electricity in cathode
Tankage ratio is (1~80):(10~99).
4) it is cured to be dried to obtain lead carbon battery composite negative pole life pole piece；Solidification temperature is 10~100 DEG C, and relative humidity is
10~100%, hardening time is 1~50h；Drying temperature is 10~200 DEG C, and relative humidity is 0~80%, and drying time is
0.1~for 24 hours.
(3) simultaneously mixed type negative plate and lead-acid battery positive plate combo, and with partition plate that pole piece is mutually isolated, structure in being mixed in
Build interior mixed interior and mixed type lead carbon battery.
That is the preparation process of lead-acid battery positive plate：
1) auxiliary material, staple fiber and lead powder are pressed into (0.1~20):(0.1~10):(50~99) mass ratio uses mixer
It is mixed, the rotating speed of agitating paddle is 10~50000 revs/min, and mixing time is 0.1~500min；Auxiliary material is barium sulfate, humic
One or both of acid；Staple fiber is one or both of polypropylene fibre, acrylic fiber, and length is 1~10mm；
2) water and sulfuric acid are added in into the mixture that step 1) obtains, is sufficiently stirred and prepares lead plaster；The density of sulfuric acid is
1.05~1.85g/cm3(25 DEG C), addition account for the 1~30% of mixture quality, and the addition of water accounts for the 0.5 of mixture quality
~50%；
3) lead plaster is scratched onto grid, it is cured to be dried to obtain interior mixed type lead carbon battery composite negative pole life pole piece；Raw pole
On piece active material thickness is 0.1~10mm；Solidification temperature is 10~100 DEG C, and relative humidity is 10~100%, hardening time
For 1~50h；Drying temperature is 10~200 DEG C, and relative humidity is 0~80%, drying time for 0.1~for 24 hours.
Beneficial effects of the present invention：
(1) it is according to the present invention it is interior it is mixed in and mixed type lead carbon superbattery, the lead-acid battery cathode part in cathode
It is replaced with interior mixed type lead carbon battery cathode, the sulfation of lead-acid battery cathode part can be effectively prevented from, improve battery
Deep discharge ability；
(2) there are many structure types with capacitance electrode for interior mixed type cathode in being mixed in and in mixed type lead carbon superbattery cathode
And compatibility mode, it disclosure satisfy that different application demands；
(3) in being mixed in and mixed type lead carbon superbattery is compared with interior mixed type lead carbon battery, interior and type lead carbon battery, is had
Longer charge and discharge circulation life.
Description of the drawings
Interior mixed interior and mixed type lead carbon battery the charge and discharge circulation life test knot that Fig. 1 cathode employing mode one is laid out
Fruit；
Interior mixed interior and mixed type lead carbon battery the charge and discharge circulation life test knot that Fig. 2 cathode employing mode two is laid out
Fruit；
Interior mixed interior and mixed type lead carbon battery the charge and discharge circulation life test knot that Fig. 3 cathode employing mode three is laid out
Fruit；
Interior mixed interior and mixed type lead carbon battery the charge and discharge circulation life test knot that Fig. 4 cathode employing mode four is laid out
Fruit；
The charge and discharge circulation life test result of type lead carbon battery is mixed in Fig. 5；
The charge and discharge circulation life test result of the interior simultaneously type lead carbon batteries of Fig. 6；
The charge and discharge circulation life test result of Fig. 7 lead-acid batteries.
Specific embodiment
The following examples will be further described the present invention, but right not thereby limiting the invention will
It asks.
The chemical conversion of lead carbon battery involved by following embodiments and performance characterization method are as follows：
(1) lead carbon battery first has to be melted into before performance test.The chemical conversion program of 5.2Ah lead carbon batteries such as following table institute
Show：
| It charges | Electric discharge | It charges | Electric discharge | It charges | |
| Electric current (mA) | 500 | 400 | 500 | 400 | 500 |
| Time (h) | 10 | 3 | 8 | 3 | 15 |
(2) battery 10h rates capacity is according to GBT22473-2008《Energy storage lead-acid accumulator》Defined method is surveyed
Examination；
(3) battery charging and discharging cycle life is according to GC-R46011：2010《Energy storage lead-acid accumulator certification code fo practice
(third edition)》Defined method is tested.
Embodiment 1
Weigh modified activated carbon base compound additive 2g, barium sulfate 0.5g, the polypropene staple 0.05g that length is 2mm
It with lead powder 100g, is premixed with high shear agitation machine, the rotating speed of agitating paddle is 39000 revs/min, mixing time 5min.
10g water and density 1.25g/cm are added in into obtained mixture3For sulfuric acid 3g, it is sufficiently stirred to obtain lead plaster.Lead plaster is scratched
Onto grid, active material thickness is 1.5mm on raw pole piece, cured to be dried to obtain lead carbon battery composite negative pole life pole piece.Gu
It is 50 DEG C to change temperature, and curing room relative humidity is 90~100%, and hardening time is for 24 hours；Drying temperature is 80 DEG C, hothouse phase
It is to humidity<30%, drying time 8h.Activated carbon 85g, conductive agent 10g and binding agent 5g are weighed, is uniformly mixed and obtains charcoal
Cream；Obtained carbon paste is coated on negative electrode grid, carbon paste coated weight is 0.03g/cm2.The activated carbon negative electrode plate of preparation is existed
Dry 12h at 80 DEG C.Then type lead carbon battery negative plate and 2 super capacitor anode plates and 3 lead-acid batteries will be mixed in 2
Positive plate combo, pole piece is mutually isolated with AGM partition plates, and interior and 3 positive 4 negative single lattice lead carbon battery of mixed type is mixed in structure.It prepares
After interior mixed interior and mixed type lead carbon battery chemical conversion, its 10h rates capacity, charge acceptance and cycle life is tested.Fig. 1 is shown
Interior mixed interior and mixed type lead carbon battery charge and discharge circulation life test result.Interior mixed interior and mixed type lead carbon manufactured in the present embodiment
The preceding rate capacity of 10h three times of battery respectively reaches 5.39Ah, 5.75Ah, 5.76Ah.Its charge acceptance reaches 1.95A, is
2.87 times of lead-acid battery (comparative example 3), 1.47 times of interior mixed type lead carbon battery (comparative example 1), (comparison of interior and type lead carbon battery
Example 2) 1.23 times.Its charge and discharge circulation life reaches 168 times, is 5.09 times of lead-acid battery (comparative example 3), interior mixed type lead carbon
1.93 times of battery (comparative example 1), it is interior and 1.98 times type lead carbon battery (comparative example 2).
Embodiment 2
Weigh modified activated carbon base compound additive 2g, barium sulfate 0.5g, the polypropene staple 0.05g that length is 2mm
It with lead powder 100g, is premixed with high shear agitation machine, the rotating speed of agitating paddle is 39000 revs/min, mixing time 5min.
10g water and density 1.25g/cm are added in into obtained mixture3For sulfuric acid 3g, it is sufficiently stirred to obtain lead plaster.Lead plaster is scratched
On to grid in 50% grid, active material thickness is 1.5mm on raw pole piece.It weighs activated carbon 85g, conductive agent 10g and glues
Agent 5g is tied, is uniformly mixed and obtains carbon paste；Obtained carbon paste is coated on negative electrode grid, carbon paste coated weight is by for 0.03g/cm2。
It is cured to be dried to obtain lead carbon battery composite negative pole life pole piece.Solidification temperature is 50 DEG C, curing room relative humidity for 90~
100%, hardening time is for 24 hours；Drying temperature is 80 DEG C, and hothouse relative humidity is<30%, drying time 8h.It will be in 4
In mixed and mixed type negative plate and 3 lead-acid battery positive plate combos, pole piece is mutually isolated with AGM partition plates, mixed in structure it is interior simultaneously
3 positive 4 negative single lattice lead carbon battery of mixed type.Preparation lead carbon battery chemical conversion after, test its 10h rates capacity, charge acceptance and
Cycle life.Fig. 2 is shown as interior mixed interior and mixed type lead carbon battery charge and discharge circulation life test prepared by the present embodiment
As a result.Interior mixed interior and mixed type lead carbon battery the preceding rate capacity of 10h three times is respectively 5.11Ah prepared by the present embodiment,
5.45Ah 5.24Ah.Its charge acceptance is 1.85A, is 2.72 times of lead-acid battery (comparative example 3), interior mixed type lead carbon electricity
1.4 times of pond (comparative example 1), it is interior and 1.17 times type lead carbon battery (comparative example 2).Its charge and discharge circulation life reaches 131 times,
It is 3.97 times of lead-acid battery (comparative example 3), 1.51 times of interior mixed type lead carbon battery (comparative example 1), interior and type lead carbon battery is (right
Ratio 2) 1.54 times.
Embodiment 3
Weigh modified activated carbon base compound additive 2g, barium sulfate 0.5g, the polypropene staple 0.05g that length is 2mm
It with lead powder 100g, is premixed with high shear agitation machine, the rotating speed of agitating paddle is 39000 revs/min, mixing time 5min.
10g water and density 1.25g/cm are added in into obtained mixture3For sulfuric acid 3g, it is sufficiently stirred to obtain lead plaster.Lead plaster is scratched
Onto grid, active material thickness is 1.5mm on raw pole piece, cured to be dried to obtain lead carbon battery composite negative pole life pole piece.Gu
It is 50 DEG C to change temperature, and curing room relative humidity is 90~100%, and hardening time is for 24 hours；Drying temperature is 80 DEG C, hothouse phase
It is to humidity<30%, drying time 8h.Activated carbon 85g, conductive agent 10g and binding agent 5g are weighed, is uniformly mixed and obtains charcoal
Cream；Obtained carbon paste is coated on standby negative plate double-sided surface, carbon paste coated weight is 0.015g/cm2.By the surface of preparation
Negative plate coated with carbon paste dry 12h at 80 DEG C obtains interior mixed interior and mixed type negative plate.Then in being mixed in 4 simultaneously
Mixed type negative plate and 3 lead-acid battery positive plate combos, pole piece is mutually isolated with AGM partition plates, and interior and mixed type 3 is mixed in structure
Positive 4 negative single lattice lead carbon battery.After the lead carbon battery chemical conversion of preparation, its 10h rates capacity, charge acceptance and Xun Huan longevity are tested
Life.Fig. 3 show interior mixed interior and mixed type lead carbon battery charge and discharge circulation life test result prepared by the present embodiment.This reality
It is respectively 5.14Ah, 5.66Ah, 5.72Ah to apply interior mixed interior and mixed type lead carbon battery the preceding rate capacity of 10h three times prepared by example.
Its charge acceptance is 2.1A, is 3.09 times of lead-acid battery (comparative example 3), interior mixed type lead carbon battery (comparative example 1)
It is 1.59 times, interior and 1.33 times type lead carbon battery (comparative example 2).Its charge and discharge circulation life reaches 151 times, is lead-acid battery
4.58 times of (comparative example 3), it is 1.74 times of interior mixed type lead carbon battery (comparative example 1), interior and type lead carbon battery (comparative example 2)
1.78 again.
Embodiment 4
Activated carbon 85g, conductive agent 10g and binding agent 5g are weighed, is uniformly mixed and obtains carbon paste；Obtained carbon paste is coated to
On negative electrode grid, carbon paste coated weight is 0.03g/cm2.The activated carbon negative electrode plate of preparation at 80 DEG C is dried into 12h, obtains activity
Charcoal pole plate.Weigh modified activated carbon base compound additive 2g, barium sulfate 0.5g, length be 2mm polypropene staple 0.05g and
Lead powder 100g, it is premixed with high shear agitation machine, the rotating speed of agitating paddle is 39000 revs/min, mixing time 5min.To
15g water and density 1.25g/cm are added in obtained mixture3For sulfuric acid 3g, it is sufficiently stirred to obtain lead plaster.Lead plaster blade coating is arrived
On the double-sided surface of activated carbon composites, the coated weight of unilateral lead plaster is g/cm2, it is cured be dried to obtain it is interior it is mixed in and mixed type bear
Pole plate.Solidification temperature is 50 DEG C, and curing room relative humidity is 90~100%, and hardening time is for 24 hours；Drying temperature is 80 DEG C, is done
Dry room relative humidity is<30%, drying time 8h.Then interior and mixed type negative plate and 3 pieces of lead-acid batteries will mixed just in 4 pieces
Pole plate combo, pole piece is mutually isolated with AGM partition plates, and interior and 3 positive 4 negative single lattice lead carbon battery of mixed type is mixed in structure.The lead of preparation
After carbon battery chemical conversion, its 10h rates capacity, charge acceptance and cycle life is tested.Fig. 4 is shown in prepared by the present embodiment
Mixed interior and mixed type lead carbon battery charge and discharge circulation life test result.Interior mixed interior and mixed type lead carbon prepared by the present embodiment
The preceding rate capacity of 10h three times of battery is respectively 5.49Ah, 5.69Ah, 5.69Ah.Its charge acceptance is 1.74A, is plumbic acid
2.56 times of battery (comparative example 3), 1.32 times of interior mixed type lead carbon battery (comparative example 1), interior and type lead carbon battery (comparative example 2)
1.1 times.Its charge and discharge circulation life reaches 120 times, is 3.64 times of lead-acid battery (comparative example 3), interior mixed type lead carbon battery
1.38 times of (comparative example 1), it is interior and 1.41 times type lead carbon battery (comparative example 2).
Comparative example 1
By 100g lead powder, 1.5g modified activated carbons, 1.4g barium sulfate, the polypropene staple height that 0.05g length is 5mm
Fast mixer is premixed.14g deionized waters are added in into the powder of premix while stirring.After stirring evenly, delay while stirring
Slow that the sulfuric acid 7.1g that density is 1.40g/mL (25 DEG C) is added dropwise, the temperature of control material persistently stirs 10min and obtains not higher than 65 DEG C
To lead plaster.By on lead plaster blade coating to metallic lead grid, lead carbon battery negative plate is obtained through dry solidification.40 DEG C of solidification temperature, Gu
It is 80% to change room humidity, hardening time 20h；Drying temperature is 80 DEG C, and hothouse relative humidity is<30%, drying time is
24h.By 3 positive plates and 4 negative plate combos, using GM membranes, it is assembled into 3 positive 4 negative 5.2Ah and mixes type lead carbon battery.Fig. 5
It show the charge and discharge circulation life test result of interior mixed type lead carbon battery.Interior mixed type lead carbon battery prepared by this comparative example
The preceding rate capacity of 10h three times is respectively 5.79Ah, 5.96Ah, 5.95Ah, charge acceptance 1.32A, charge and discharge circulation life
Reach 87 times.
Comparative example 2
100g lead powder, 1.4g barium sulfate, the polypropene staple that 0.05g length is 5mm are carried out in advance with homogenizer
It is mixed.14g 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 7.1g 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, curing room humidity are
80%, hardening time 20h；Drying temperature is 80 DEG C, and hothouse relative humidity is<30%, drying time is for 24 hours.By activity
Charcoal, conductive agent and binding agent are according to mass ratio 85:10:5 are uniformly mixed, and obtain carbon paste；Obtained carbon paste is coated to negative plate
On grid, carbon paste coated weight is 0.03g/cm2.The activated carbon negative electrode plate of preparation at 80 DEG C is dried into 12h, obtains ultracapacitor
Negative plate.Then by 2 lead-acid battery cathode plates and 2 super capacitor anode plates and 3 lead-acid battery positive plate combos, pole
Piece is mutually isolated with AGM partition plates, the interior simultaneously 3 positive 4 negative single lattice lead carbon battery of type of structure.After the lead carbon battery chemical conversion of preparation, it is tested
10h rates capacity, charge acceptance and cycle life.In Fig. 6 is shown and the charge and discharge circulation life of type lead carbon battery is tested
As a result.10h rates capacity is respectively 5.74Ah, 5.46Ah, 5.51Ah three times before interior and type lead carbon battery prepared by this comparative example,
Charge acceptance is 1.58A, and charge and discharge circulation life reaches 85 times.
Comparative example 3
100g lead powder, 1.4g barium sulfate, the polypropene staple that 0.05g length is 5mm are carried out in advance with homogenizer
It is mixed.14g 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 7.1g 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 plate is obtained through dry solidification.40 DEG C of solidification temperature, curing room humidity are
80%, hardening time 20h；Drying temperature is 80 DEG C, and hothouse relative humidity is<30%, drying time is for 24 hours.By 3 just
Pole plate and 4 negative plate combos using GM membranes, are assembled into 3 positive 4 negative 5.2Ah lead-acid batteries.Fig. 7 show 5.2Ah plumbic acids electricity
The charge and discharge circulation life test result in pond.10h rates capacity is respectively three times before 5.2Ah lead-acid batteries prepared by this comparative example
5.72Ah, 5.45Ah, 5.24Ah, charge acceptance 0.68A, charge and discharge circulation life are 33 times.
Claims (3)
1. interior and mixed type lead carbon superbattery is mixed in one kind；Including cathode and lead-acid battery positive plate, membrane and shell,
The cathode (refers to the plumbic acid electricity mixed with carbon material by ultracapacitor activated carbon electrodes and interior mixed type lead carbon battery cathode
Pond cathode) it is formed in parallel；Wherein interior mixed type lead carbon battery cathode refers to the lead-acid battery cathode mixed with carbon material.
2. according to interior mixed interior and mixed type lead carbon superbattery described in claim 1, which is characterized in that
Battery structure layout specifically includes one of following four layout type：
(1) mode one：It mixes inside electric with type lead carbon is mixed in ultracapacitor activated carbon electrodes piece partial replacement in type lead carbon battery
Pond negative plate, mix in composition in and mixed type lead carbon superbattery；
(2) mode two：Type lead carbon battery cathode lead plaster is mixed in filling in negative electrode grid Partial Mesh, fills and lives in remaining grid
Property charcoal, mix in composition in and mixed type negative plate；In being mixed in preparation and mixed type negative plate is matched somebody with somebody with lead-acid battery positive plate
Group, the two are separated with partition plate, and interior and mixed type lead carbon superbattery is mixed in composition；
(3) mode three：Type lead-acid battery cathode plate unilateral or bilateral surface coating activated carbon is mixed inside, is mixed interior in composition and is mixed
Type negative plate, then with lead-acid battery positive plate combo, the two separates with partition plate, mixed in composition in and the super electricity of mixed type lead carbon
Pond；
(4) mode four：Type lead carbon battery cathode lead plaster is mixed in the coating of ultracapacitor activated carbon electrodes unilateral or bilateral surface,
In being mixed in composition and mixed type negative plate, then with lead-acid battery positive plate combo, the two separates with partition plate, mixed in composition in simultaneously
Mixed type lead carbon superbattery.
3. a kind of interior mixed interior and mixed type lead carbon superbattery cathode preparation method of claim 1 or 2, the cathode bag
It includes：A, one of method in B, C, D is prepared,
A, the preparation method of the interior mixed type lead carbon battery negative plate involved by layout type one, comprises the following steps：
1) modified 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 using mixer；Auxiliary material is one or both of barium sulfate, humic acid；Short fibre
It ties up as one or both of polypropylene fibre, acrylic fiber, length is 1~10mm；
2) water and sulfuric acid are added in into the mixture that step 1) obtains, is sufficiently stirred and prepares lead plaster；The density of sulfuric acid for 1.05~
1.85g/cm3(25 DEG C), addition account 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 interior mixed type lead carbon battery composite negative pole life pole piece；On raw pole piece
Active material thickness is 0.1~10mm；Solidification temperature is 10~100 DEG C, and relative humidity is 10~100%, hardening time for 1~
50h；Drying temperature is 10~200 DEG C, and relative humidity is 0~80%, drying time for 0.1~for 24 hours；
The modified activated carbon base compound additive refers to the active carbon particle containing metallic element, the specific surface area of active carbon particle
For 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 or more, content is 0.01~30wt% in additive；
The preparation method of ultracapacitor activated carbon electrodes piece involved by layout type one, comprises the following steps：
1) by activated carbon, conductive agent and binding agent according to mass ratio (50~95):(1~30):(1~20) it is uniformly mixed, obtains
Carbon paste；One or two or more kinds in conductive agent acetylene black, conductive carbon black, graphite powder；Binding agent for butadiene-styrene rubber, PTFE,
One or two or more kinds in PVDF；
2) carbon paste for obtaining step 1) is coated on negative electrode grid, and carbon paste coated weight is by for 0.01~1g/cm2；
3) the ultracapacitor activated carbon negative electrode plate for preparing step 2) dry 0.1 at 20~200 DEG C~for 24 hours；
B, the preparation method of the interior mixed type lead carbon battery cathode portion involved by layout type two, comprises the following steps：
1) lead plaster described in A is scratched into the Partial Mesh of negative electrode grid；Blade coating thickness of the lead plaster in Partial Mesh is 0.1
~10mm；
2) carbon paste described in A is coated on negative electrode grid in remaining grid, carbon paste coated weight is 0.01~1g/cm2；Carbon paste
Coated area is determined with lead plaster coated area than the battery capacity by cathode and capacitance ratio；The capacitance and battery of cathode
Capacity Ratio is (1~80):(10~99)；
3) cure and be dried to obtain in mixed simultaneously mixed type negative plate；Solidification temperature is 10~100 DEG C, and relative humidity is 10~100%,
Hardening time is 1~50h；Drying temperature is 10~200 DEG C, and relative humidity is 0~80%, drying time for 0.1~for 24 hours；
C, the preparation method of the interior mixed type lead carbon battery cathode portion involved by layout type three, comprises the following steps：
1) carbon paste described in A is coated to described in A on the unilateral or bilateral surface of interior mixed type lead carbon battery negative plate；Carbon paste applies
The amount of covering is determined by the battery capacity of cathode with capacitance ratio；Cathode capacitance is (1~80) with battery capacity ratio:(10~
99)；
2) by upper step) negative plate for preparing dry 0.1 at 20~200 DEG C~for 24 hours；
D, the preparation method of the electrode of super capacitor part involved by layout type four, comprises the following steps：
1) lead plaster described in A is scratched onto the unilateral or bilateral surface of the plate of ultracapacitor activated carbon negative electrode described in A；Carbon paste
Coated weight is determined by the battery capacity of cathode with capacitance ratio；Capacitance and battery capacity ratio are (1~80) in cathode:
(10~99)；
It is cured to be dried to obtain lead carbon battery composite negative pole life pole piece；Solidification temperature is 10~100 DEG C, relative humidity for 10~
100%, hardening time is 1~50h；Drying temperature is 10~200 DEG C, and relative humidity is 0~80%, drying time for 0.1~
24h。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108123103A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | It is graphitized activated carbon base compound additive and preparation and lead carbon battery cathode and application |
| CN111261841A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Lead-carbon battery electrode and preparation and application thereof |
| CN111261840A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Integrated lead-carbon battery carbon electrode and preparation and application thereof |
| CN111525195A (en) * | 2019-02-01 | 2020-08-11 | 骆驼集团蓄电池研究院有限公司 | Maintenance-free lead-acid storage battery with excellent deep cycle life and production method thereof |
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| CN104599852A (en) * | 2013-10-30 | 2015-05-06 | 张彩欣 | Super capacitor battery and manufacturing method thereof |
| CN105280394A (en) * | 2014-06-27 | 2016-01-27 | 西南大学 | Multilayer structure-based novel battery type supercapacitor with high power density and high energy density and preparation method |
| CN105788872A (en) * | 2006-12-12 | 2016-07-20 | 联邦科学及工业研究组织 | Improved energy storage device |
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| CN105788872A (en) * | 2006-12-12 | 2016-07-20 | 联邦科学及工业研究组织 | Improved energy storage device |
| CN104599852A (en) * | 2013-10-30 | 2015-05-06 | 张彩欣 | Super capacitor battery and manufacturing method thereof |
| CN105280394A (en) * | 2014-06-27 | 2016-01-27 | 西南大学 | Multilayer structure-based novel battery type supercapacitor with high power density and high energy density and preparation method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108123103A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | It is graphitized activated carbon base compound additive and preparation and lead carbon battery cathode and application |
| CN111261841A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Lead-carbon battery electrode and preparation and application thereof |
| CN111261840A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Integrated lead-carbon battery carbon electrode and preparation and application thereof |
| CN111261841B (en) * | 2018-11-30 | 2021-01-05 | 中国科学院大连化学物理研究所 | Lead-carbon battery electrode and preparation and application thereof |
| CN111261840B (en) * | 2018-11-30 | 2021-02-26 | 中国科学院大连化学物理研究所 | Integrated lead-carbon battery carbon electrode and preparation and application thereof |
| CN111525195A (en) * | 2019-02-01 | 2020-08-11 | 骆驼集团蓄电池研究院有限公司 | Maintenance-free lead-acid storage battery with excellent deep cycle life and production method thereof |
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