CN110400907A - A kind of preparation method of external application formula lead carbon battery cathode - Google Patents
A kind of preparation method of external application formula lead carbon battery cathode Download PDFInfo
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- CN110400907A CN110400907A CN201910495953.2A CN201910495953A CN110400907A CN 110400907 A CN110400907 A CN 110400907A CN 201910495953 A CN201910495953 A CN 201910495953A CN 110400907 A CN110400907 A CN 110400907A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of preparation method of external application formula lead carbon battery cathode, the cathode includes the active carbon layer of external application formula, protects the gel electrolyte layer of layer of charcoal.The pole plate is made of lead plaster (lead powder, humic acid, staple fiber, barium sulfate, sodium lignin sulfonate, acetylene black, sulfuric acid, pure water) and layer of charcoal.By the way that suitable binder is added in prepared by layer of charcoal, and layer of charcoal is compacted with suitable pressure to strengthen the physical connectivity between charcoal phase and lead phase and the charge transport ability on lead-carbon interface in polar board surface.By the way that gel electrolyte is coated in the polar board surface containing layer of charcoal, achieve the purpose that layer of charcoal is protected to prevent the layer of charcoal liberation of hydrogen that falls off and inhibit.The charge acceptance of cathode can be improved by the pole plate that layer of charcoal of the invention forms, active material effective rate of utilization alleviates the cathode sulfation phenomenon under high magnification partial state of charge, improves the power density and cycle life of battery entirety.
Description
Technical field:
The present invention relates to a kind of lead carbon batteries, form more particularly to a kind of cathode of lead carbon battery.
Background technique:
With gradually popularizing for electrified equipment, demand of the people to energy storage device increasingly increases.Possess closely as one kind
The energy storage device of two one-hundred-year histories, lead-acid battery have that at low cost, low-temperature stability is good, the advantages such as safe and reliable.But its energy
The disadvantage that density is low, cycle life is short causes application range to receive restriction.
Lead carbon battery is known as next-generation lead-acid battery, it is that carbon material is added in lead-acid battery cathode.Due to carbon materials
Material has good electric conductivity, the chemical stability in strong acid environment, much higher than the specific surface area of pure lead, with traditional lead acid batteries
It compares, lead carbon battery cathode sulfation is significantly inhibited, and negative electrode active material effective rate of utilization is significantly improved,
Whole cycle life and energy density are obviously reinforced.Lead carbon battery is the state-of-the-art technology in lead-acid battery field, is international new energy
The emphasis direction of source energy storage industry has wide development space.
As a kind of novel lead-acid battery, for lead carbon battery while enjoying many advantages, there is also some problems.By
There is very big difference in partial size, density in carbon material and lead powder, directly it is uneven to will cause mixing for addition, and then influences electricity
Pond stability.By that will have the multistage pore canal carbon material of electric double layer capacitance characteristic, ionic conduction characteristic to be coated in Plante-type plate table
Face is made to fully demonstrate the difunctional combination electrode of lead charcoal of capacitance characteristic and faradic battery characteristic, is a kind of effective
Solution route.
Different from internal-mixing and outer and formula lead carbon battery, it is highly conductive that external application carbon material can more give full play to carbon material
Rate, high-specific surface area, in high concentrated acid chemical stability advantage, and then more effectively inhibit sulfation, improve active material
Effective rate of utilization, but the connectivity of carbon material and Plante-type plate is still the main problem faced at present.In lead carbon battery high magnification
When partial state of charge cycle charge-discharge, due to the lower overpotential of hydrogen evolution of carbon material and the electrode environment of concentrated acid, high temperature, institute
The carbon material of coating easily falls off from electrode surface, leads to battery performance decline even short circuit.The connectivity of carbon material and lead particle
Problem needs to solve.
Patent CN101667637 discloses a kind of method for manufacturing lead-carbon ultracapacitor battery cathode, will with lead powder be mainly at
Point active material and the different zones of electrode matrix are respectively coated with active carbon active material as main component, then dry
It is dry, lead-carbon ultracapacitor battery cathode is made.The invention is by avoiding lead and carbon from avoiding carbon material in the accumulation in three-dimensional
It falls off.Patent CN 102856528A discloses a kind of preparation method of super storage battery lead-carbon negative plate, first that carbon paste is uniform
It is coated in lead negative raw cook two sides, the pole plate for being coated with carbon paste is wrapped up in tightly with coated plate paper bag then, pressure compacting is carried out to it, so
Afterwards by the pole plate after compacting 45-120 DEG C at a temperature of be dried 1-2 hours, pass through physical bonds power and improve carbon material
Connectivity.However, these patents have been concerned only with physical force and structure design between lead-carbon, carbon and electrolyte are had ignored
Between interaction, thus connectivity problem does not generally solve still.
Summary of the invention:
The purpose of the present invention is to provide a kind of negative plate of lead-carbon battery of stable external application carbon material, are being applied to
When battery, negative terminal surface carbon material long-time stable structure, degree of sulfation is significantly reduced, active material effective rate of utilization
It significantly improves, the service life cycle under high magnification partial state of charge significantly extends.
For this purpose, the invention adopts the following technical scheme:
A kind of preparation method of negative plate of lead-carbon battery, at least includes the following steps:
(1) preparation of carbon paste
The mixing material of the first Carbon Materials of 70-90wt%, 5-15wt% bridging agent, 5-15wt% conductive carbon material is soaked
Not in ethyl alcohol, it is heated to 75-85 DEG C, heated at constant temperature stirs 0.5-1.5h, until being made convenient for natural cooling after the viscosity of coating
Carbon paste；First Carbon Materials are specific surface area 1500-2500m2The active carbon or specific surface area 100-500m of/g2The graphite of/g
Charcoal；
(2) preparation of gel
The polymer solids of 5-10wt% are added in deionized water, be heated to 60-90 DEG C and are subject to constant temperature stirring, 2-8h
Transparent uniform gel electrolyte is obtained afterwards；
(3) preparation of lead plaster
By the lead powder of 70-85wt%, the humic acid of 0.5-3wt%, the staple fiber of 0.5-3wt%, 0.5-3wt% sulfuric acid
Barium, the sodium lignin sulfonate of 0.5-3wt%, the acetylene black of 0.5-3wt% are uniformly mixed, are slow added into 5.0-10.0wt%'s
The sulfuric acid of deionized water and 5-10wt% are stirred evenly into lead plaster；The sulfuric acid concentration is 4-5mol/L；
(4) preparation of negative plate of lead-carbon battery
The lead plaster of step (3) preparation is first coated on metal grid, is prepared into green plate after dry solidification, it later will step
Suddenly the carbon paste of (1) preparation is according to 0.1-1g/cm2Load capacity be evenly applied to green plate surface, with the pressure compaction of 1-5MPa,
Dry 6-24h, obtains the layer of charcoal under natural environment, and gel electrolyte obtained in step (2) is pressed 0.1-1g/cm2's
Load capacity is coated in above-mentioned electrode surface, and negative plate of lead-carbon battery is made in dry 12-48h under natural environment.
Bridging agent is the one or more of polystyrene, polyacrylonitrile, polytetrafluoroethylene (PTFE) in the step (1).
Conductive Carbon Materials include one or more of graphene, carbon black, aquadag in the step (1).
Polymer includes one or more of polyethylene oxide, polyvinyl alcohol, polyaniline in the step (2).
Step (2) middle short fiber is one or more of terylene, acrylic fibers, fibre length about 1-40mm.
In the step (4) the step of dry solidification are as follows:
1) 50 DEG C, air humidity 95-98%, constant temperature 20-30h；
2) 55 DEG C, air humidity 70-90%, constant temperature 10-20h；
3) 60 DEG C, air humidity 20-40%, constant temperature 1-5h；
4) 70 DEG C, air humidity 20-40%, constant temperature 1-5h.
In the further preferred step (4) the step of dry solidification are as follows:
1) 50 DEG C, air humidity 98%, constant temperature is for 24 hours；
2) 55 DEG C, air humidity 80%, constant temperature 15h；
3) 60 DEG C, air humidity 30%, constant temperature 3h；
4) 70 DEG C, air humidity 30%, constant temperature 3h.
The utility model has the advantages that the present invention is by selecting the composition of above-mentioned certain material, by each raw material self-characteristic and mutually
The analysis of effect has carried out a large amount of test, especially by above-mentioned corresponding specific preparation process, enhances carbon material and lead
The connectivity of pole plate, appearance is closely knit after polar plate solidification, and intensity improves many than conventional plates, and anti-drop ability compares commonsense method
The dual pole plate raising being made is more, and etching extent is also less, and layer of charcoal and lead plaster are combined closely, and hole is more, and internal resistance is smaller,
The combination advantage of carbon material electric double layer performance Yu lead material faraday's reaction is given full play to, and then more effectively inhibits sulfuric acid
Salinization improves active material effective rate of utilization, and significantly extends the service life cycle under high magnification partial state of charge.Have
The lead charcoal battery of this negative plate has more wide application prospect in start and stop automobile, solar energy, wind energy energy storage field.
Detailed description of the invention
Fig. 1: the testing impedance of embodiment 1 and common plumbic acid pole plate comparison；
Fig. 2: the cyclic voltammetry of embodiment 1 and common plumbic acid pole plate comparison；
Below with reference to embodiment, the present invention will be further described:
Embodiment 1:
It is 2000m by 70g specific surface area2The active carbon of/g, 10g graphite, 15g the mixing material of polyacrylonitrile be immersed in
In dehydrated alcohol, 85 DEG C are heated to, heated at constant temperature stirs 1h, until carbon paste is made convenient for natural cooling after the viscosity of coating；
The ethylene oxide solid of 3g is added in 47g water, be heated to 60 DEG C and is subject to constant temperature stirring, is obtained after 8h transparent equal
One gel electrolyte；
By the lead powder of 100g, the humic acid of 0.5g, the 40mm polyester staple fiber of 0.83g, the barium sulfate of 0.8g, 0.2g wood
Quality sodium sulfonate, 0.2g acetylene black be uniformly mixed active material is made, mixed active material is successively slowly added to 10.5g
Water and the 4.7mol/L sulfuric acid (rate of addition 2mL/s) of 8.3g stir evenly lead plaster be made；
The lead plaster of preparation is first coated on 4*7cm metal grid, is prepared into green plate after dry solidification, it later will preparation
Carbon paste according to 0.3g/cm2Load capacity be evenly applied to green plate surface, with the pressure compaction of 5MPa, done under natural environment
Gel electrolyte obtained is pressed 0.1g/cm by dry 6h2Load capacity be coated in above-mentioned electrode surface, it is dry under natural environment
Negative plate of lead-carbon battery is made in 48h.
Steps are as follows for dry solidification:
1) 50 DEG C, air humidity 98%, constant temperature is for 24 hours
2) 55 DEG C, air humidity 80%, constant temperature 15h
3) 60 DEG C, air humidity 30%, constant temperature 3h
4) 70 DEG C, air humidity 30%, constant temperature 3h.
Embodiment 2:
By 85g specific surface area 100m2The graphite of/g, 10g acetylene black, the mixing material of polytetrafluoroethylene (PTFE) of 5g are immersed in nothing
In water-ethanol, 85 DEG C are heated to, heated at constant temperature stirs 1h, until carbon paste is made convenient for natural cooling after the viscosity of coating；By 5g's
Polyaniline solids are added in 50g water, are heated to 90 DEG C and are subject to constant temperature stirring, obtain transparent uniform gel electrolyte after 2h；
By the lead powder of 100g, the humic acid of 0.5g, the 40mm polyester staple fiber of 0.83g, the barium sulfate of 0.8g, 0.2g wood
Quality sodium sulfonate, 0.2g acetylene black be uniformly mixed active material is made, mixed active material is successively slowly added to 10.5g
Water and the 4.7mol/L sulfuric acid (rate of addition 2mL/s) of 8.3g stir evenly lead plaster be made；
The lead plaster of preparation is first coated on 4*7cm metal grid, is prepared into green plate after dry solidification, it later will preparation
Carbon paste according to 0.3g/cm2Load capacity be evenly applied to green plate surface, with the pressure compaction of 1MPa, done under natural environment
Gel electrolyte obtained is pressed 0.5g/cm by dry 6h2Load capacity be coated in above-mentioned electrode surface, it is dry under natural environment
Lead carbon battery negative plates are made in 48h.
Steps are as follows for dry solidification:
1) 50 DEG C, air humidity 98%, constant temperature is for 24 hours
2) 55 DEG C, air humidity 80%, constant temperature 15h
3) 60 DEG C, air humidity 30%, constant temperature 3h
4) 70 DEG C, air humidity 30%, constant temperature 3h.
Embodiment 3:
By 80g specific surface area 100m2The active carbon of/g, 10g acetylene black, 10g polytetrafluoroethylene (PTFE) mixing material submergence
In dehydrated alcohol, 75 DEG C are heated to, heated at constant temperature stirs 1h, until carbon paste is made convenient for natural cooling after the viscosity of coating；It will
4g polyvinylalcohol solids are added in 50g water, are heated to 90 DEG C and are subject to constant temperature stirring, obtain transparent uniform gel electrolyte after 2h
Matter；
By the lead powder of 100g, the humic acid of 0.5g, the 40mm polyester staple fiber of 0.83g, the barium sulfate of 0.8g, 0.2g wood
Quality sodium sulfonate, 0.2g acetylene black be uniformly mixed active material is made, mixed active material is successively slowly added to 10.5g
Water and the 4.7mol/L sulfuric acid (rate of addition 2mL/s) of 8.3g stir evenly lead plaster be made；
The lead plaster of preparation is first coated on 4*7cm metal grid, is prepared into green plate after dry solidification, it later will preparation
Carbon paste according to 0.3g/cm2Load capacity be evenly applied to green plate surface, with the pressure compaction of 2MPa, done under natural environment
Gel electrolyte obtained is pressed 0.5g/cm by dry 10h2Load capacity be coated in above-mentioned electrode surface, it is dry under natural environment
Lead carbon battery negative plates are made in 48h.
Steps are as follows for dry solidification:
1) 50 DEG C, air humidity 98%, constant temperature is for 24 hours
2) 55 DEG C, air humidity 80%, constant temperature 15h
3) 60 DEG C, air humidity 30%, constant temperature 3h
4) 70 DEG C, air humidity 30%, constant temperature 3h.
Lead charcoal cathode made from embodiment 1 is subjected to standard three electrode testing impedance, is platinum electrode, reference electrode to electrode
For mercury/Mercurous sulfate electrode, electrolyte is 5.0M sulfuric acid.As shown in Figure 1, the charge-transfer resistance of the pole plate added with carbon material
Do not change significantly, but ion diffusion resistance is substantially reduced, be on the one hand due to being added to carbon material in one side surface of pole plate,
The charge transfer impedance being electrochemically reacted inside pole plate is not adversely affected, on the other hand due to the electrolysis of carbon material
Liquid storage effect and the building of electric double layer accelerate the adsorption and desorption speed of ion in the transmission rate and solid liquid interface of ion
Rate.Therefore on electrochemical impedance spectroscopy, lead carbon battery negative plate obtained by example 1 embodies more excellent mass transfer impedance.
But the addition of layer of charcoal is remarkably decreased the load transfer resistance of lead carbon battery cathode obtained, illustrates the charcoal layer formula in lead-
Necessity that electric conductivity on charcoal interface is also improved.
Lead charcoal cathode made from embodiment 1 is subjected to standard three electrode cyclic voltammetry, is platinum electrode, reference to electrode
Electrode is mercury/Mercurous sulfate electrode, and electrolyte is 5.0M sulfuric acid.As shown in Fig. 2, compared with conventional lead acid battery pole plate, example 1
Lead carbon battery negative plate obtained shows higher redox peak height and bigger redox peak area, and due to
The width of the synergistic effect of layer of charcoal and lead plaster, peak broadens, and embodies some capacitance characteristics in shape.The test shows that example 1 is made
The lead carbon battery negative plate obtained has stronger charge acceptance and discharge capability, higher active material utilization, institute's group
At battery have better power-performance.But the introducing of carbon material, the liberation of hydrogen for inevitably reducing pole plate are excessively electric
Position, illustrates that the carbon-coating and gel layer formula still have necessity of promotion in terms of liberation of hydrogen inhibition.
Lead charcoal cathode obtained in embodiment 2,3 embodies and conclusion similar in embodiment 1 in electro-chemical test:
I.e. the mass transfer resistance of obtained lead charcoal cathode significantly reduces, and there is no significant changes for load transfer resistance.Obtained lead charcoal is negative
The charging of pole, the power-performance of electric discharge have a distinct increment, and embody certain battery, capacitor double function characteristic.Obtained lead
Charcoal cathode still has necessity of promotion in terms of the electric conductivity on inhibition liberation of hydrogen, lead-charcoal interface.
Claims (7)
1. a kind of preparation method of external application formula lead carbon battery cathode, it is characterised in that: at least include the following steps:
(1) preparation of carbon paste
The mixing material of the first Carbon Materials of 70-90wt%, 5-15wt% bridging agent, 5-15wt% conductive carbon material is soaked completely
Not in ethyl alcohol, it is heated to 75-85 DEG C, heated at constant temperature stirs 0.5-1.5h, until being made convenient for natural cooling after the viscosity of coating
Carbon paste；First Carbon Materials are specific surface area 1500-2500m2The active carbon or specific surface area 100-500m of/g2The graphite of/g
Charcoal；
(2) preparation of gel
The polymer solids of 5-10wt% are added in deionized water, be heated to 60-90 DEG C and are subject to constant temperature stirring, after 2-8h
To transparent uniform gel electrolyte；
(3) preparation of lead plaster
By the lead powder of 70-85wt%, the humic acid of 0.5-3wt%, the staple fiber of 0.5-3wt%, 0.5-3wt% barium sulfate,
The sodium lignin sulfonate of 0.1-3wt%, the acetylene black of 0.1-3wt% are uniformly mixed, and are slow added into going for 5.0-10.0wt%
The sulfuric acid of ionized water and 5-10wt% stir evenly, and lead plaster is made；The sulfuric acid concentration is 4-5mol/L；
(4) preparation of negative plate of lead-carbon battery
The lead plaster of step (3) preparation is first coated on metal grid, green plate is prepared into after dry solidification, later by step
(1) carbon paste prepared is according to 0.1-1g/cm2Load capacity be evenly applied to green plate surface, with the pressure compaction of 1-5MPa, from
Dry 6-24h, obtains the layer of charcoal under right environment, and gel electrolyte obtained in step (2) is pressed 0.1-1g/cm2It is negative
Carrying capacity is coated in above-mentioned electrode surface, and negative plate of lead-carbon battery is made in dry 12-48h under natural environment.
2. a kind of preparation method of external application formula lead carbon battery cathode according to claim 1, it is characterised in that: the step
Suddenly in (1) bridging agent be polystyrene, polyacrylonitrile, polytetrafluoroethylene (PTFE) one or more.
3. a kind of preparation method of external application formula lead carbon battery cathode according to claim 1, it is characterised in that: the step
Suddenly conductive Carbon Materials include one or more of graphene, carbon black, aquadag in (1).
4. a kind of preparation method of external application formula lead carbon battery cathode according to claim 1, it is characterised in that: the step
Suddenly polymer used in (2) includes one or more of polyethylene oxide, polyvinyl alcohol, polyaniline.
5. a kind of preparation method of external application formula lead carbon battery cathode according to claim 1, it is characterised in that: the step
Suddenly (3) middle short fiber is one or more of terylene, acrylic fibers, fibre length about 1-40mm.
6. a kind of preparation method of external application formula lead carbon battery cathode according to claim 1, it is characterised in that: the step
Suddenly in (4) the step of dry solidification are as follows:
1) 50 DEG C, air humidity 95-98%, constant temperature 20-30h；
2) 55 DEG C, air humidity 70-90%, constant temperature 10-20h；
3) 60 DEG C, air humidity 20-40%, constant temperature 1-5h；
4) 70 DEG C, air humidity 20-40%, constant temperature 1-5h.
7. a kind of preparation method of negative plate of lead-carbon battery according to claim 6, it is characterised in that: the step
(4) in the step of dry solidification are as follows:
1) 50 DEG C, air humidity 98%, constant temperature is for 24 hours；
2) 55 DEG C, air humidity 80%, constant temperature 15h；
3) 60 DEG C, air humidity 30%, constant temperature 3h；
4) 70 DEG C, air humidity 30%, constant temperature 3h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111081986A (en) * | 2019-12-09 | 2020-04-28 | 吉林省凯禹电化学储能技术发展有限公司 | Preparation method of high-power external application type lead-carbon battery cathode |
| CN111668456A (en) * | 2020-05-12 | 2020-09-15 | 吉林省凯禹电化学储能技术发展有限公司 | External application type lead-carbon start-stop battery negative plate and preparation method thereof and battery |
| CN111710835A (en) * | 2020-06-12 | 2020-09-25 | 吉林省凯禹电化学储能技术发展有限公司 | Preparation method of long-life external-application lead-carbon battery cathode |
| CN113506683A (en) * | 2020-06-12 | 2021-10-15 | 吉林大学 | Lead-carbon supercapacitor cathode and preparation method thereof |
| CN113764627A (en) * | 2021-08-09 | 2021-12-07 | 安徽理士电源技术有限公司 | Formula and preparation method of high-performance lead-carbon battery negative electrode lead paste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111081986A (en) * | 2019-12-09 | 2020-04-28 | 吉林省凯禹电化学储能技术发展有限公司 | Preparation method of high-power external application type lead-carbon battery cathode |
| CN111668456A (en) * | 2020-05-12 | 2020-09-15 | 吉林省凯禹电化学储能技术发展有限公司 | External application type lead-carbon start-stop battery negative plate and preparation method thereof and battery |
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| CN111710835A (en) * | 2020-06-12 | 2020-09-25 | 吉林省凯禹电化学储能技术发展有限公司 | Preparation method of long-life external-application lead-carbon battery cathode |
| CN113506683A (en) * | 2020-06-12 | 2021-10-15 | 吉林大学 | Lead-carbon supercapacitor cathode and preparation method thereof |
| CN111710835B (en) * | 2020-06-12 | 2022-01-14 | 吉林省凯禹电化学储能技术发展有限公司 | Preparation method of long-life external-application lead-carbon battery cathode |
| CN113506683B (en) * | 2020-06-12 | 2022-09-13 | 吉林大学 | Lead-carbon supercapacitor cathode and preparation method thereof |
| CN113764627A (en) * | 2021-08-09 | 2021-12-07 | 安徽理士电源技术有限公司 | Formula and preparation method of high-performance lead-carbon battery negative electrode lead paste |
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