CN108682851A - A kind of energy storage diachylon of negative electrode of lead carbon battery and preparation method thereof - Google Patents
A kind of energy storage diachylon of negative electrode of lead carbon battery and preparation method thereof Download PDFInfo
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- CN108682851A CN108682851A CN201810573384.4A CN201810573384A CN108682851A CN 108682851 A CN108682851 A CN 108682851A CN 201810573384 A CN201810573384 A CN 201810573384A CN 108682851 A CN108682851 A CN 108682851A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to lead carbon battery field, a kind of energy storage diachylon of negative electrode of lead carbon battery and preparation method thereof is disclosed, cathode lead plaster includes the component of following parts by weight：100 parts of lead powder, 6 ~ 9 parts of sulfuric acid, 8 ~ 13 parts of deionized water, 0.5 ~ 1.0 part of barium sulfate, 0.1 ~ 0.3 part of lignin, 0.1 ~ 0.5 part of graphite, 0.1 ~ 0.3 part of carbon black, 0.01 ~ 0.10 part of stearic acid, 0.2 ~ 0.5 part of polyethylene glycol, 0.5 ~ 1.0 part of activated carbon, 0.1 ~ 0.6 part of the graphene nanometer sheet of doped carbon nanometer pipe, 0.01 ~ 0.06 part of indium oxide, 0.08 ~ 0.15 part of staple fiber.The present invention reaches the charge acceptance that can improve battery, slows down cathode sulfation by the cathode lead plaster formula and preparation method thereof of improvement lead carbon battery, and can reduce the water loss of battery, further extends the actual life of lead carbon battery.
Description
Technical field
The present invention relates to lead carbon battery field more particularly to a kind of energy storage diachylon of negative electrode of lead carbon battery and its preparation sides
Method.
Background technology
Compared to common VRLA accumulators, energy storage lead carbon battery is due to having capacitance characteristic, and charge acceptance is high, high power
Rate discharge performance is superior, and sulfuric-resisting salinization ability is strong, is current extremely potential energy storage lead the advantages that having extended cycle life
Acid accumulator.Lead carbon battery negative plate generally adds the carbon material of high level, and the carbon material specific surface area being added（BET）Very
Height can enhance the charge acceptance of battery, to slow down cathode sulfation.But different carbon material impurities are not
Together, containing the impurity for reducing hydrogen Evolution overpotential in some carbon materials, with the increase of carbon material additive amount in battery cathode,
The evolving hydrogen reaction that battery cathode can correspondingly be increased causes battery to fail because dehydration is excessive, can reduce lead charcoal to a certain extent
The actual life of battery.
In order to reduce the water loss of energy storage lead carbon battery, battery manufacturers or user generally use stringent charging system
Degree, by reducing rate of charge（Charging and discharging ratio）Method, to reduce the evolving hydrogen reaction of cathode.But this can often make again
At the undercharge of battery, lead to the sulfation of battery pole plates, therefore needs periodically continually to carry out equalizaing charge to battery.So
And with the use condition of existing energy storage lead carbon battery, it is difficult to execute this stringent and cumbersome charging system, actually use
Service life is extremely difficult to expected design, objectively limits popularization and application of the lead carbon battery in energy storage field.
If by improving the cathode lead plaster formula of lead carbon battery, reaches the charge acceptance that can improve battery, subtract
Slow cathode sulfation, and the water loss of battery can be reduced, the actual life of lead carbon battery is further increased, for continuing
The performance for improving energy storage lead carbon battery, is of great practical significance.
Invention content
In order to solve the above technical problem, the present invention provides a kind of energy storage diachylon of negative electrode of lead carbon battery and its preparation sides
Method, the present invention reach the charging that can improve battery by the cathode lead plaster formula and preparation method thereof of improvement lead carbon battery
By ability, slow down cathode sulfation, and the water loss of battery can be reduced, further extends the actual use longevity of lead carbon battery
Life.
The specific technical solution of the present invention is：A kind of energy storage diachylon of negative electrode of lead carbon battery, includes the group of following parts by weight
Point：
100 parts of lead powder,
6 ~ 9 parts of sulfuric acid,
8 ~ 13 parts of deionized water,
0.5 ~ 1.0 part of barium sulfate,
0.1 ~ 0.3 part of lignin,
0.1 ~ 0.5 part of graphite,
0.1 ~ 0.3 part of carbon black,
0.01 ~ 0.10 part of stearic acid,
0.2 ~ 0.5 part of polyethylene glycol,
0.5 ~ 1.0 part of activated carbon,
0.1 ~ 0.6 part of the graphene nanometer sheet of doped carbon nanometer pipe,
0.01 ~ 0.06 part of indium oxide,
0.08 ~ 0.15 part of staple fiber.
The present invention increases cathode by adding the indium oxide that there is hydrogen inhibiting effect is precipitated in lead carbon battery cathode
The overpotential that hydrogen is precipitated can effectively reduce cell water loss, prevent battery from failing because dehydration is excessive, extend battery
Cycle life；Meanwhile it being also added with the graphene nanometer sheet of doped carbon nanometer pipe, it both ensure that the high-specific surface area of carbon material,
The high conductivity of graphene is utilized again, further enhances the charge acceptance of battery, it is negative effectively to slow down lead carbon battery
The sulfation of pole significantly improves the service life of energy storage lead carbon battery.In addition, containing stearic acid in the present invention, can subtract
The oxidation rate of spongy lead, can further improve the service life of battery in slow negative plate.
Preferably, the oxidizability of the lead powder is 72-78%.
Preferably, the density of the sulfuric acid is 1.400 ± 0.005g/cm3；The carbon black is acetylene carbon black；It is described poly-
Ethylene glycol is polyethylene glycol 400.
Polyethylene glycol is limited to polyethylene glycol 400, can be used as binder, can be played between lead powder and related addition
Cementation greatly strengthens the linking intensity between lead powder and various additives.
Preferably, the graphite is anisotropic graphite.
Preferably, the preparation method of the graphene nanometer sheet of the doped carbon nanometer pipe is：By graphene oxide and carbon
Nanotube 2.5-3.5 in mass ratio:1 mixing, it is uniform to first pass through ultrasonic wave dispersion mixing, then carries out electronation, most passes through afterwards
Cross the graphene nanometer sheet that doped carbon nanometer pipe is made in rotary evaporation.
Preferably, the staple fiber is length is 3-5mm, the polyester fiber of a diameter of 3 ~ 5 Denier.
Preferably, the polyester fiber is modified polyester fibre, preparation method is：
A）By weight by 20-30 parts of 100 parts of polyester polyol, 35-45 parts of ethanedioic acid, 0.1-0.5 parts of p-methyl benzenesulfonic acid and water
It is added in reactor, is warming up to 200-210 DEG C, react 1.5-2.5h, ethanedioic acid sealing end is made in the reaction was continued after vacuumizing 5-6h
Polyester polyol；
B）The polyester polyol 10-20 for by weight blocking 90-100 parts of terephthalic acid (TPA), 40-50 parts of ethylene glycol and ethanedioic acid
Esterification is carried out at 240 ~ 260 DEG C, 0.2 ~ 0.5MPa in part input reaction kettle, then adds catalyst 260~280
DEG C, polycondensation reaction is carried out under 40 ~ 1000 Pa, modified poly ester master batch is made in underwater cutpellet；
C）By weight by the 75-85 parts of mixing of 15-25 parts of modified poly ester master batch and polyester slice, it is made by conventional spinning processes
Modified polyester fibre.
In the prior art, the effect that staple fiber is added in lead plaster is reinforcing lead plaster, makes its consolidation without fugitive, former
Reason is similar with root system of plant reinforcing soil.Wherein polyester staple fiber is staple fiber commonly used in the art.The present invention is basic herein
On, polyester fiber is modified, conductive characteristic is made it have, is had the technical effect that, staple fiber is uniformly distributed in lead plaster, is handed over
Paramnesia is at network.If the network has good electric conductivity, it will be able to cooperatively form conductive mesh jointly with other conductive materials
Network, to further increase the electric conductivity of lead plaster.
According to the method described above modified polyester fibre obtained its with conductive characteristic, sheet resistance is 107Ω/sq water
It is flat.In the above-mentioned methods, the polyester polyol of the ethanedioic acid sealing end with hydrophilic electroconductive characteristic is first prepared, then poly- with polyester monocase
It closes and modified poly ester master batch is made, when polyester master particle and conventional polyester slice co-blended spinning, hydrophilic electroconductive material is in fiber surface
It is distributed in fine tendon shape, forms conductive surface layer.
A kind of preparation method of energy storage diachylon of negative electrode of lead carbon battery, includes the following steps：
（1）By deionized water inject mixing equipment in, under stirring, sequentially add lignin, barium sulfate, carbon black, graphite,
Activated carbon, the graphene nanometer sheet of doped carbon nanometer pipe, indium oxide are made suspending liquid A, continue to stir, spare；Suspending liquid A exists
State is continuously stirred using preceding holding.
（2）It by polyethylene glycol injection heating device, is then stirred under state, stearic acid is added and continuously stirs, wait for hard
After resin acid is completely dissolved into polyethylene glycol, obtained solution B keeps the temperature at 70 ~ 90 DEG C solution B spare.
（3）Lead powder is added in paste mixing machine, staple fiber, stirring is added；Under stirring, by suspending liquid A addition and cream
In machine；After suspending liquid A adds, under stirring, solution B is added in paste mixing machine, adds and continues to stir.
（4）Under stirring, sulfuric acid is injected into paste mixing machine, sulfuric acid continues to stir after adding.
（5）Progress and cream in paste mixing machine, control lead plaster temperature≤60 DEG C；It waits for that lead plaster temperature is down to≤45 DEG C, measures lead
Cream apparent density meets 4.55 ± 0.05g/cm3, otherwise, it is adjusted until symbol by adding deionized water or increasing mixing time
It is combined into only.
Traditional lead plaster preparation method is after lead powder is added in paste mixing machine, generally first by barium sulfate, lignin, charcoal
The additives such as black, graphite, activated carbon, fiber be added paste mixing machine in, with lead powder carry out dry state stirring a period of time, add from
Sub- water continues stirring and prepares lead plaster.Since lead powder is different from the density that various additives are mutual, dry state stirring
Under, distribution of the additive in lead plaster is extremely difficult to uniformity.Lead plaster preparation method in the present invention, first by deionized water,
Suspension is made in the additives such as lignin, barium sulfate, carbon black, graphite, activated carbon, graphene nanometer sheet, indium oxide, then gradually adds
Enter and be stirred mixing in lead powder, keeps lead plaster mixing evenly consistent.
Preferably, step（3）In, detailed process is：Lead powder is added in paste mixing machine, staple fiber, stirring 3 ~ 6 is added
min；Under stirring, in 2 ~ 5min, suspending liquid A is added in paste mixing machine；After suspending liquid A adds, under stirring,
In 1 ~ 3min, solution B is added in paste mixing machine, adds and continues 4 ~ 8min of stirring.
Preferably, step（4）In, in 13 ~ 18min, sulfuric acid is injected into paste mixing machine, sulfuric acid continues stirring 10 after adding
~15min。
It is compared with the prior art, the beneficial effects of the invention are as follows：
（1）, the present invention diachylon of negative electrode of lead carbon battery increase the overpotential of cathode hydrogen precipitation due to being added to indium oxide,
Cell water loss can be effectively reduced, prevents battery from failing because dehydration is excessive, extends the cycle life of battery.
（2）, the present invention in graphene nanometer sheet, doped with carbon nanotube.The graphene nanometer sheet is by graphite oxide
Alkene adds carbon nanotube, is made by disperseing reduction evaporation, the reunion between graphene sheet layer can be effectively prevent compound, have height
Specific surface area, and the high conductivity with remote superactive carbon, further enhance the charge acceptance of battery, effectively slow down
The sulfation of lead carbon battery cathode, significantly improves the service life of energy storage lead carbon battery.
（3）, the present invention in lead plaster preparation method, first by deionized water, lignin, barium sulfate, carbon black, graphite, activity
Suspension is made in the additives such as charcoal, graphene nanometer sheet, indium oxide, then is gradually added into lead powder and is stirred mixing, makes lead plaster
Mixing is evenly consistent.And traditional lead plaster preparation method, after lead powder is added in paste mixing machine, generally first by barium sulfate, wood
The additives such as quality, carbon black, graphite, activated carbon, fiber are added in paste mixing machine, are carried out dry state stirring a period of time with lead powder, then
Deionized water is added, continues stirring and prepares lead plaster.Since lead powder is different from the density that various additives are mutual, dry state
Under stirring, distribution of the additive in lead plaster is extremely difficult to uniformity.
（4）, the present invention in contain stearic acid, the oxidation rate of spongy lead in negative plate can be slowed down, can further improve
The service life of battery.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Total embodiment
A kind of energy storage diachylon of negative electrode of lead carbon battery, includes the component of following parts by weight：
Oxidizability is 100 parts of the lead powder of 72-78%,
1.400±0.005g/cm36 ~ 9 parts of sulfuric acid,
8 ~ 13 parts of deionized water,
0.5 ~ 1.0 part of barium sulfate,
0.1 ~ 0.3 part of lignin,
0.1 ~ 0.5 part of anisotropic graphite,
0.1 ~ 0.3 part of acetylene carbon black,
0.01 ~ 0.10 part of stearic acid,
0.2 ~ 0.5 part of polyethylene glycol 400,
0.5 ~ 1.0 part of activated carbon,
0.1 ~ 0.6 part of the graphene nanometer sheet of doped carbon nanometer pipe,
0.01 ~ 0.06 part of indium oxide,
Length is 0.08 ~ 0.15 part of the polyester fiber of 3-5mm, a diameter of 3 ~ 5 Denier.
Wherein, the preparation method of the graphene nanometer sheet of the doped carbon nanometer pipe is：By graphene oxide and carbon nanometer
Manage 2.5-3.5 in mass ratio:1 mixing, it is uniform to first pass through ultrasonic wave dispersion mixing, electronation is then carried out, finally through overwinding
Turn the graphene nanometer sheet that doped carbon nanometer pipe is made in evaporation.
Optionally, the polyester fiber is modified polyester fibre, and preparation method is：
A）By weight by 20-30 parts of 100 parts of polyester polyol, 35-45 parts of ethanedioic acid, 0.1-0.5 parts of p-methyl benzenesulfonic acid and water
It is added in reactor, is warming up to 200-210 DEG C, react 1.5-2.5h, ethanedioic acid sealing end is made in the reaction was continued after vacuumizing 5-6h
Polyester polyol；
B）The polyester polyol 10-20 for by weight blocking 90-100 parts of terephthalic acid (TPA), 40-50 parts of ethylene glycol and ethanedioic acid
Esterification is carried out at 240 ~ 260 DEG C, 0.2 ~ 0.5MPa in part input reaction kettle, then adds catalyst 260~280
DEG C, polycondensation reaction is carried out under 40 ~ 1000 Pa, modified poly ester master batch is made in underwater cutpellet；
C）By weight by the 75-85 parts of mixing of 15-25 parts of modified poly ester master batch and polyester slice, it is made by conventional spinning processes
Modified polyester fibre.
The preparation method of above-mentioned energy storage diachylon of negative electrode of lead carbon battery, includes the following steps：
（1）By deionized water inject mixing equipment in, under stirring, sequentially add lignin, barium sulfate, carbon black, graphite,
Activated carbon, the graphene nanometer sheet of doped carbon nanometer pipe, indium oxide are made suspending liquid A, continue to stir, spare；Suspending liquid A exists
State is continuously stirred using preceding holding.
（2）It by polyethylene glycol injection heating device, is then stirred under state, stearic acid is added and continuously stirs, wait for hard
After resin acid is completely dissolved into polyethylene glycol, obtained solution B keeps the temperature at 70 ~ 90 DEG C solution B spare.
（3）Lead powder is added in paste mixing machine, staple fiber is added, stirs 3 ~ 6 min；Under stirring, in 2 ~ 5min,
Suspending liquid A is added in paste mixing machine；After suspending liquid A adds, under stirring, in 1 ~ 3min, paste mixing machine is added in solution B
It is interior, it adds and continues 4 ~ 8min of stirring.
（4）Under stirring, in 13 ~ 18min, sulfuric acid is injected into paste mixing machine, sulfuric acid continue after adding stirring 10 ~
15min。
（5）Progress and cream in paste mixing machine, control lead plaster temperature≤60 DEG C；It waits for that lead plaster temperature is down to≤45 DEG C, measures lead
Cream apparent density meets 4.55 ± 0.05g/cm3, otherwise, it is adjusted until symbol by adding deionized water or increasing mixing time
It is combined into only.
Embodiment 1
The preparation of the graphene nanometer sheet of doped carbon nanometer pipe：By graphene oxide and carbon nanotube in mass ratio 3:1 mixing, first
It is uniform by ultrasonic wave dispersion mixing, electronation is then carried out, the stone that doped carbon nanometer pipe is made in rotary evaporation is finally passed through
Black alkene nanometer sheet.
Its technical parameter is as follows：
| Detection project | Testing result | Detection method |
| Graphene content（wt.%） | 66.7±0.2 | / |
| Content of carbon nanotubes（wt.%） | 33.3±0.2 | / |
| Graphene nanometer sheet piece passes through（mm） | 5~15 | GB/T 19077.1 |
| Ash content（wt.%） | ≤0.5 | GB/T 3521-95 |
| Moisture（wt.%） | ≤0.5 | GB/T 6283 |
Weigh following raw material：Lead powder（Oxidizability：72%~78%）1000Kg, sulfuric acid solution（1.400±0.005g/cm3）Additive amount
It is the 8.5% of lead powder, deionized water（The μ S/cm of conductivity≤2）Additive amount is the 11% of lead powder, barium sulfate（Fineness：Cross 325 mesh sieve
Residue≤0.10%）Additive amount is the 0.55% of lead powder, and lignin additive amount is the 0.25% of lead powder, graphite（High-purity eudialyte
Ink）Additive amount is the 0.15% of lead powder, carbon black（Acetylene carbon black）Additive amount is the 0.2% of lead powder, stearic acid（It analyzes pure）Additive amount
It is the 0.05% of lead powder, polyethylene glycol（PEG400）Additive amount is the 0.3% of lead powder, and activated carbon additive amount is the 0.5% of lead powder, is mixed
The graphene nanometer sheet additive amount of miscellaneous carbon nanotube is the 0.25% of lead powder, and high-purity indium oxide additive amount is the 0.02% of lead powder, fine
Dimension（Polyester fiber, 3 ~ 5mm of length；3 ~ 5 Denier of diameter）Additive amount is the 0.08% of lead powder.
Method is prepared as follows and prepares lead plaster：
（1）, by deionized water inject special equipment in, under stirring, sequentially add lignin, barium sulfate, carbon black, stone
Ink, activated carbon, graphene nanometer sheet, indium oxide.After all adding, suspending liquid A is made, continues stirring 2 ~ 5 hours, can make
With.Suspending liquid A is continuously stirring state using preceding holding.
（2）, by polyethylene glycol PEG400 injection heating devices, be then stirred under state, stearic acid be added, and continuously stirs
It mixes.Wait for that stearic acid is completely dissolved into（Without block）In PEG400, obtained solution B.It can be used when solution B reaches 80 DEG C.
（3）, by lead powder be added paste mixing machine in, be added fiber, stir 5min.In the case where continuing stirring, in 3.5min,
Suspending liquid A is added in paste mixing machine.After suspending liquid A adds, in the case where continuing stirring, in 2min, paste mixing machine is added in solution B
It is interior, it adds and continues to stir 6min.
（4）, under stirring, in 15min, dilute sulfuric acid is injected into paste mixing machine.After dilute sulfuric acid adds, continue to stir
12min。
（5）, entire lead plaster preparation process, control lead plaster temperature≤60 DEG C.When lead plaster temperature is down to≤45 DEG C, lead is measured
Cream apparent density meets 4.55 ± 0.05g/cm3, can come into operation.Otherwise, by adding deionized water or increasing mixing time
It is adjusted.
The test cell of embodiment 1：Obtained cathode lead plaster, for the negative of OPzV energy storage tubular colloidal lead carbon battery
Pole plate manufactures, and by coated plate, solidification, drying, divides brushing piece, then assembly production is at OPzV energy storage graphene tubular type leaching colloidal charcoal
Battery.
Embodiment 2
The preparation of the graphene nanometer sheet of doped carbon nanometer pipe：By graphene oxide and carbon nanotube in mass ratio 3.5:1 mixing,
It is uniform to first pass through ultrasonic wave dispersion mixing, then carries out electronation, finally passes through rotary evaporation and doped carbon nanometer pipe is made
Graphene nanometer sheet.
Weigh following raw material：Lead powder（Oxidizability：72%~78%）1000Kg, sulfuric acid solution（（1.400±0.005g/cm3））
Additive amount is the 8.5% of lead powder, deionized water（The μ S/cm of conductivity≤2）Additive amount is the 11% of lead powder, barium sulfate（Fineness：It crosses
325 mesh sieve residue≤0.10%）Additive amount is the 0.55% of lead powder, and lignin additive amount is the 0.25% of lead powder, graphite（It is high-purity
Anisotropic graphite）Additive amount is the 0.15% of lead powder, carbon black（Acetylene carbon black）Additive amount is the 0.2% of lead powder, stearic acid（It analyzes pure）
Additive amount is the 0.05% of lead powder, polyethylene glycol（PEG400）Additive amount is the 0.3% of lead powder, and activated carbon additive amount is lead powder
0.5%, the graphene nanometer sheet additive amount of doped carbon nanometer pipe is the 0.2% of lead powder, indium oxide（It analyzes pure）Additive amount is lead powder
0.015%, fiber（Polyester fiber, 3 ~ 5mm of length；3 ~ 5 Denier of diameter）Additive amount is the 0.08% of lead powder.
Preparation method presses embodiment 1.
The experimental cell of embodiment 2：Obtained cathode lead plaster, for the negative of OPzV energy storage tubular colloidal lead carbon battery
Pole plate manufactures, and by coated plate, solidification, drying, divides brushing piece, then assembly production is at OPzV energy storage graphene tubular type leaching colloidal charcoal
Battery.
Embodiment 3
The preparation of the graphene nanometer sheet of doped carbon nanometer pipe：By graphene oxide and carbon nanotube in mass ratio 3:1 mixing, first
It is uniform by ultrasonic wave dispersion mixing, electronation is then carried out, the stone that doped carbon nanometer pipe is made in rotary evaporation is finally passed through
Black alkene nanometer sheet.
The preparation of modified polyester fibre：A）By weight by 100 parts of polyester polyol, 40 parts of ethanedioic acid, p-methyl benzenesulfonic acid
0.3 part and 25 parts of water are added in reactors, are warming up to 205 DEG C, react 2h, the reaction was continued after vacuumizing 5.5h, and ethanedioic acid is made
The polyester polyol of sealing end.
B）By weight by 15 parts of inputs of polyester polyol of 95 parts of terephthalic acid (TPA), 45 parts of ethylene glycol and ethanedioic acid sealing end
Esterification is carried out in reaction kettle at 250 DEG C, 0.35MPa, then it is anti-to carry out polycondensation at 270 DEG C, 500Pa for addition catalyst
It answers, underwater cutpellet, modified poly ester master batch is made；
C）By weight by the 80 parts of mixing of 20 parts of modified poly ester master batch and polyester slice, Modified Polyester is made by conventional spinning processes
Synthetic fibre fiber.
Weigh following raw material：Lead powder（Oxidizability：72%~78%）1000Kg, sulfuric acid solution（1.400±0.005g/cm3）Add
Dosage is the 8.5% of lead powder, deionized water（The μ S/cm of conductivity≤2）Additive amount is the 11% of lead powder, barium sulfate（Fineness：Cross 325
Mesh sieves residue≤0.10%）Additive amount is the 0.55% of lead powder, and lignin additive amount is the 0.25% of lead powder, graphite（High-purity opposite sex
Graphite）Additive amount is the 0.15% of lead powder, carbon black（Acetylene carbon black）Additive amount is the 0.2% of lead powder, stearic acid（It analyzes pure）Addition
Amount is the 0.05% of lead powder, polyethylene glycol（PEG400）Additive amount is the 0.3% of lead powder, and activated carbon additive amount is the 0.5% of lead powder,
The graphene nanometer sheet additive amount of doped carbon nanometer pipe is the 0.25% of lead powder, and high-purity indium oxide additive amount is the 0.02% of lead powder,
Fiber（Modified polyester fibre, 3 ~ 5mm of length；3 ~ 5 Denier of diameter）Additive amount is the 0.08% of lead powder.
Method is prepared as follows and prepares lead plaster：
（1）, by deionized water inject special equipment in, under stirring, sequentially add lignin, barium sulfate, carbon black, stone
Ink, activated carbon, graphene nanometer sheet, indium oxide.After all adding, suspending liquid A is made, continues stirring 2 ~ 5 hours, can make
With.Suspending liquid A is continuously stirring state using preceding holding.
（2）, by polyethylene glycol PEG400 injection heating devices, be then stirred under state, stearic acid be added, and continuously stirs
It mixes.Wait for that stearic acid is completely dissolved into（Without block）In PEG400, obtained solution B.It can be used when solution B reaches 80 DEG C.
（3）, by lead powder be added paste mixing machine in, be added fiber, stir 5min.In the case where continuing stirring, in 3.5min,
Suspending liquid A is added in paste mixing machine.After suspending liquid A adds, in the case where continuing stirring, in 2min, paste mixing machine is added in solution B
It is interior, it adds and continues to stir 6min.
（4）, under stirring, in 15min, dilute sulfuric acid is injected into paste mixing machine.After dilute sulfuric acid adds, continue to stir
12min。
（5）, entire lead plaster preparation process, control lead plaster temperature≤60 DEG C.When lead plaster temperature is down to≤45 DEG C, lead is measured
Cream apparent density meets 4.55 ± 0.05g/cm3, can come into operation.Otherwise, by adding deionized water or increasing mixing time
It is adjusted.
The test cell of embodiment 3：Obtained cathode lead plaster, for the negative of OPzV energy storage tubular colloidal lead carbon battery
Pole plate manufactures, and by coated plate, solidification, drying, divides brushing piece, then assembly production is at OPzV energy storage graphene tubular type leaching colloidal charcoal
Battery.
Comparative example 1
The cathode lead plaster formula of 1 lead carbon battery of comparative example is as follows：
Lead powder（Oxidizability：72%~78% ）1000Kg,
Sulfuric acid（1.400±0.005g/cm3）85Kg,
Deionized water（The μ S/cm of conductivity≤2）110 Kg,
5.5 Kg of barium sulfate,
2.5 Kg of lignin,
Graphite（High-purity opposite sex graphite）1.5 Kg,
Carbon black（Acetylene carbon black）2 Kg,
5 Kg of activated carbon,
Fiber（Polyester fiber, 3 ~ 5mm of length）0.8 Kg.
The preparation method of 1 diachylon of negative electrode of lead carbon battery of comparative example is as follows：
（1）, lead powder is first added in paste mixing machine, add fiber, barium sulfate, lignin, carbon black, graphite, activated carbon, then stir
Mix 5 min.In the case where continuing stirring, in 3min, deionized water is added in paste mixing machine.
（2）, under stirring, in 15min, will dilute sulfuric acid inject paste mixing machine in.After dilute sulfuric acid adds, continue to stir
12min。
（3）, entire lead plaster preparation process, control lead plaster temperature≤60 DEG C.When lead plaster temperature is down to≤45 DEG C, lead is measured
Cream apparent density meets 4.55 ± 0.05g/cm3, can come into operation.Otherwise, by adding deionized water or increasing mixing time
It is adjusted.
Battery performance detects,
The comparison of embodiment 1 and comparative example 1：
100%DOD cycle lives 200 times, 1 lead carbon battery weightlessness 169g of embodiment, 1 lead carbon battery weightlessness 705g of comparative example are implemented
1 battery weightlessness of example reduces by 76% than 1 battery of comparative example, the significant decrease of battery fluid loss, it is meant that extend battery cycle life
Provide guarantee.
When 100%DOD cycle lives 800 times, the residual capacity of 1 lead carbon battery of embodiment is 106%C10（Rated capacity）, right
The residual capacity of 1 lead carbon battery of ratio is 93%C10（Rated capacity）, 1 lead carbon battery residual capacity of embodiment is than 1 battery of comparative example
High by 13%, the cycle life of 1 lead carbon battery of embodiment is substantially better than common batteries.
The comparison of embodiment 2 and comparative example 1：
100%DOD cycle lives 200 times, 2 lead carbon battery weightlessness 237g of embodiment, 1 lead carbon battery weightlessness 705g of comparative example are implemented
2 lead carbon battery weightlessness of example reduces by 66% than common batteries, the significant decrease of battery fluid loss, it is meant that extend the circulating battery longevity
Life provides guarantee.
When 100%DOD cycle lives 800 times, the residual capacity of 2 lead carbon battery of embodiment is 105%C10（Rated capacity）, right
The residual capacity of 1 lead carbon battery of ratio is 93%C10（Rated capacity）, 2 lead carbon battery residual capacity of embodiment is higher than common batteries
12%, the cycle life of two test cell of example is substantially better than common batteries.
The comparison of embodiment 3 and comparative example 1：
100%DOD cycle lives 200 times, 1 lead carbon battery weightlessness 159g of embodiment, 1 lead carbon battery weightlessness 705g of comparative example are implemented
3 battery weightlessness of example reduces by 77.5% than 1 battery of comparative example, the significant decrease of battery fluid loss, it is meant that extend the circulating battery longevity
Life provides guarantee.
When 100%DOD cycle lives 800 times, the residual capacity of 3 lead carbon battery of embodiment is 107%C10（Rated capacity）, right
The residual capacity of 1 lead carbon battery of ratio is 93%C10（Rated capacity）, 3 lead carbon battery residual capacity of embodiment is than 1 battery of comparative example
High by 14%, the cycle life of 3 lead carbon battery of embodiment is substantially better than common batteries.
It is seen by the verification result of embodiment 1-3, energy storage diachylon of negative electrode of lead carbon battery of the present invention, is effectively reduced
The water loss of battery, extends the cycle life of battery；Due to adding the graphene nanometer sheet of doped carbon nanometer pipe, both ensured
The high-specific surface area of carbon material, and the high conductivity of graphene is utilized, further enhance the charge acceptance of battery,
The sulfation for effectively slowing down lead carbon battery cathode, significantly improves the service life of energy storage lead carbon battery.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not imposed any restrictions to the present invention, every according to the present invention
Technical spirit still falls within the technology of the present invention side to any simple modification, change and equivalent transformation made by above example
The protection domain of case.
Claims (10)
1. a kind of energy storage diachylon of negative electrode of lead carbon battery, it is characterised in that include the component of following parts by weight：
100 parts of lead powder,
6 ~ 9 parts of sulfuric acid,
8 ~ 13 parts of deionized water,
0.5 ~ 1.0 part of barium sulfate,
0.1 ~ 0.3 part of lignin,
0.1 ~ 0.5 part of graphite,
0.1 ~ 0.3 part of carbon black,
0.01 ~ 0.10 part of stearic acid,
0.2 ~ 0.5 part of polyethylene glycol,
0.5 ~ 1.0 part of activated carbon,
0.1 ~ 0.6 part of the graphene nanometer sheet of doped carbon nanometer pipe,
0.01 ~ 0.06 part of indium oxide,
0.08 ~ 0.15 part of staple fiber.
2. a kind of energy storage diachylon of negative electrode of lead carbon battery as described in claim 1, which is characterized in that the oxidizability of the lead powder
For 72-78%.
3. a kind of energy storage diachylon of negative electrode of lead carbon battery as described in claim 1, which is characterized in that the density of the sulfuric acid is
1.400±0.005g/cm3；The carbon black is acetylene carbon black；The polyethylene glycol is polyethylene glycol 400.
4. a kind of energy storage diachylon of negative electrode of lead carbon battery as described in claim 1, which is characterized in that the graphite is eudialyte
Ink.
5. a kind of energy storage diachylon of negative electrode of lead carbon battery as described in claim 1, which is characterized in that the doped carbon nanometer pipe
The preparation method of graphene nanometer sheet be：By graphene oxide and carbon nanotube 2.5-3.5 in mass ratio:1 mixing, first passes through
Ultrasonic wave dispersion mixing is uniform, then carries out electronation, finally passes through the graphene that doped carbon nanometer pipe is made in rotary evaporation
Nanometer sheet.
6. a kind of energy storage diachylon of negative electrode of lead carbon battery as described in claim 1, which is characterized in that the staple fiber is length
For 3-5mm, the polyester fiber of a diameter of 3 ~ 5 Denier.
7. a kind of energy storage diachylon of negative electrode of lead carbon battery as described in claim 1, which is characterized in that the polyester fiber is to change
Property polyester fiber, preparation method are：
A）By weight by 20-30 parts of 100 parts of polyester polyol, 35-45 parts of ethanedioic acid, 0.1-0.5 parts of p-methyl benzenesulfonic acid and water
It is added in reactor, is warming up to 200-210 DEG C, react 1.5-2.5h, ethanedioic acid sealing end is made in the reaction was continued after vacuumizing 5-6h
Polyester polyol；
B）The polyester polyol 10-20 for by weight blocking 90-100 parts of terephthalic acid (TPA), 40-50 parts of ethylene glycol and ethanedioic acid
Esterification is carried out at 240 ~ 260 DEG C, 0.2 ~ 0.5MPa in part input reaction kettle, then adds catalyst 260~280
DEG C, polycondensation reaction is carried out under 40 ~ 1000 Pa, modified poly ester master batch is made in underwater cutpellet；
C）By weight by the 75-85 parts of mixing of 15-25 parts of modified poly ester master batch and polyester slice, it is made by conventional spinning processes
Modified polyester fibre.
8. a kind of preparation side of energy storage diachylon of negative electrode of lead carbon battery as described in claims 1 or 2 or 3 or 4 or 5 or 6 or 7
Method, it is characterised in that include the following steps：
（1）By deionized water inject mixing equipment in, under stirring, sequentially add lignin, barium sulfate, carbon black, graphite,
Activated carbon, the graphene nanometer sheet of doped carbon nanometer pipe, indium oxide are made suspending liquid A, continue to stir, spare；Suspending liquid A exists
State is continuously stirred using preceding holding；
（2）It by polyethylene glycol injection heating device, is then stirred under state, stearic acid is added and continuously stirs, wait for stearic acid
After being completely dissolved into polyethylene glycol, obtained solution B keeps the temperature at 70 ~ 90 DEG C solution B spare；
（3）Lead powder is added in paste mixing machine, staple fiber, stirring is added；Under stirring, suspending liquid A is added in paste mixing machine；
After suspending liquid A adds, under stirring, solution B is added in paste mixing machine, adds and continues to stir；
（4）Under stirring, sulfuric acid is injected into paste mixing machine, sulfuric acid continues to stir after adding；
（5）Progress and cream in paste mixing machine, control lead plaster temperature≤60 DEG C；It waits for that lead plaster temperature is down to≤45 DEG C, measures lead plaster and regard
Density meets 4.55 ± 0.05g/cm3, otherwise, by add deionized water or increase mixing time be adjusted until meet for
Only.
9. the preparation method of energy storage diachylon of negative electrode of lead carbon battery as described in claim 1, which is characterized in that step（3）In,
Detailed process is：Lead powder is added in paste mixing machine, staple fiber is added, stirs 3 ~ 6 min；Under stirring, in 2 ~ 5min,
Suspending liquid A is added in paste mixing machine；After suspending liquid A adds, under stirring, in 1 ~ 3min, paste mixing machine is added in solution B
It is interior, it adds and continues 4 ~ 8min of stirring.
10. the preparation method of energy storage diachylon of negative electrode of lead carbon battery as described in claim 1, which is characterized in that step（4）
In, in 13 ~ 18min, sulfuric acid is injected into paste mixing machine, sulfuric acid continues 10 ~ 15min of stirring after adding.
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