CN106129368B - Absorbent charcoal composite material, preparation method and the lead carbon battery using the absorbent charcoal composite material - Google Patents

Absorbent charcoal composite material, preparation method and the lead carbon battery using the absorbent charcoal composite material Download PDF

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CN106129368B
CN106129368B CN201610713156.3A CN201610713156A CN106129368B CN 106129368 B CN106129368 B CN 106129368B CN 201610713156 A CN201610713156 A CN 201610713156A CN 106129368 B CN106129368 B CN 106129368B
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carbon
composite material
absorbent charcoal
active carbon
graphene
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CN106129368A (en
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王建新
林昊
李亚东
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Ningbo Zhongke Energy Technology Co., Ltd.
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/06Lead-acid accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/80Particles consisting of a mixture of two or more inorganic phases
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/11Powder tap density
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/40Electric properties
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention by with open structure active carbon and graphene or/and carbon nanotube it is compound, wherein absorbent charcoal material is basic framework, and graphene or/and carbon nanotube be intercalated into the open structure of active carbon, constitutes the absorbent charcoal composite material with rock-steady structure.The absorbent charcoal composite material not only increases the mechanical structure stability of active carbon, also improves the electric conductivity of active carbon, while increasing the specific surface area of active carbon, improves the capacitor of active carbon, the characteristics such as bulk density.When the activity Carbon composites are used for lead carbon battery, mechanical structure stability, the electric conductivity of cathode are not only contributed to, additionally it is possible to which the mixing uniformity for improving cathode and lead plaster effectively improves the overall performance of lead carbon battery.

Description

Absorbent charcoal composite material, preparation method and using the absorbent charcoal composite material Lead carbon battery
Technical field
The invention belongs to active carbon, technical field of graphene more particularly to a kind of active Carbon composites, preparation method with And the lead carbon battery using the material.
Background technique
Due to the deterioration of environment, the exhaustion of traditional energy, demand of the people to new energy is gradually increased.Global range is current Each state expands the application market of new energy all in Devoting Major Efforts To Developing new energy technology energetically.The clean energy resourcies system such as wind energy, solar energy It is the new energy production capacity mode of present society mainstream, but many reasons such as discontinuity, unstability of new energy generation restrict The development of New Energy Industry, cause the energy generated that can not be effectively used, energy-storage system is as energy generation to the energy It, can be with the effective solution above problem using intermediate important link.So providing a kind of energy storage device of excellent performance becomes It is badly in need of the critical issue to be solved now.
Lead-acid battery is that current technology is the most mature, but because its cycle life is short, can not achieve large current density The many reasons such as electricity are not able to satisfy demand of the present people to energy storage device.As an improvement the plumbic acid energy-storage battery of type, lead Carbon battery can solve the shortcomings of traditional lead acid batteries, such as improve specific capacity and cycle life, improve specific discharge capacity, because And become present energy storage ideal energy storage device in the market.
Lead carbon battery is a kind of novel superbattery, is the combination of traditional lead acid batteries and supercapacitor, so Not only have the advantages of supercapacitor instantaneous large-current charge and discharge, has also played lead-acid battery low energy, inexpensive advantage. The difference of lead carbon battery and conventional batteries is to increase a certain amount of active carbon in common lead-acid battery cathode lead plaster as negative Pole plate, the addition of active carbon is so that the advantages of cathode of solar panel obtains large capacity charging, improves the utilization of active material Rate, play the role of buffering during high power charging-discharging, effective protection negative plate, it is suppressed that " sulfation " phenomenon It generates.
But the active carbon in existing lead carbon battery leads to the conduction that it is spontaneous because to obtain higher specific surface area Performance is poor, and physical structure stability is low, and the internal resistance of cell negative plate increases and battery efficiency reduces;Also, negative plate is following Basic structure destructible, leads to battery failure in ring charge and discharge process.In addition, existing carbon composite density and lead powder density There is biggish difference, makes it difficult to carbon composite is evenly dispersed.Conductive agent especially therein is mostly deposited in the form of carbon black Because of the smaller easy reunion of its particle, it is bigger to disperse difficulty.These factors drastically influence the performance of lead carbon battery, therefore It solves the problems, such as that active carbon is spontaneous and solves the problems, such as that the mixing of lead carbon paste material could more effectively promote the globality of lead carbon battery Energy.
Patent document CN101764263A discloses lead carbon superbattery containing activated carbon negative electrode and preparation method thereof, will live Property charcoal be only simply doped into the negative plate of lead carbon ribbon battery, and the spontaneous existing defect of unresolved active carbon, in lead plaster Preparation process in carbon composite doping process be not significantly improved the mixture homogeneity of lead powder and carbon composite yet Problem.
Patent document CN104124474A discloses a kind of lead carbon battery of negative plate containing high-carbon, and the usage amount of charcoal is increased to Greater than 35%, although the whole hydrogen evolution phenomenon of lead plaster negative plate is made to decrease, sulfuric acid leading crystal is inhibited to a certain degree The growth of grain, but the negative plate of high-carbon content make the mechanical mechanism of the pole plate during charge and discharge cycles of battery easily by It destroys, and the proportion of active material lead reduces and also results in the capacity of battery and be greatly lowered.In addition, lead and doping charcoal Hydrogen-evolution overpotential it is inconsistent cause its hydrogen evolution phenomenon that can aggravate, to accelerate battery failure.The patent also there is no solve lead with The mixing uniformity problem of charcoal doping.
The graphene that patent document CN104505262A is disclosed a kind of graphene lead composite material and prepared using the material Lead carbon electrode improves the porosity and electric conductivity of negative plate using graphene, but graphene cost of manufacture is high and disperses It spends low.
Patent document CN103794796A discloses lead carbon battery cathode and the preparation method and application thereof, adds in lead Carbon anode Enter graphene.But graphene is only used as a kind of simple carbon materials feed additives, wherein the dispersion of graphene does not obtain It solves, the battery performance of lead carbon battery has to the improvement of not half, does not play essence to the performance of battery and is promoted.
Summary of the invention
Status in view of the above technology, the present invention answer the active carbon with open structure with graphene or/and carbon nanotube It closes, wherein absorbent charcoal material is basic framework, and graphene or/and carbon nanotube are intercalated into the open structure of active carbon, is constituted Absorbent charcoal composite material with rock-steady structure.
In view of graphene sheet layer structure is preferably intercalated into active carbon, the piece diameter of graphene is less than 200um, carbon nanometer The pipe range of pipe is advisable less than 50um, and such graphene film diameter is smaller, and carbon nanotube pipe range is smaller, is conducive to intercalation and enters active carbon In lesser hole.
Preferably, the mass ratio of active carbon described in the quality sum of the graphene and carbon nanotube is 0.01:1-0.5:1.
Cocoanut active charcoal has many advantages, such as high mechanical strength, gap structure flourishing (based on mesoporous), large specific surface area, because This, the active carbon is preferably cocoanut active charcoal.
The absorbent charcoal composite material has the advantages that
(1) in graphene and carbon nanotube layer plane the intensity of carbon-to-carbon atom key be higher than diamond key intensity, That is, the mechanical structure stability of graphene and carbon nanotube is greater than diamond, therefore it is formed into composite material with active carbon The mechanical structure stability of conventional carbon can be effectively improved;
(2) graphene and carbon nanotube have good conductive property, and go back after it is formed composite material with active carbon The electric conductivity of conventional carbon can be increased substantially;
(3) the characteristics of high-ratio surface possessed by graphene and carbon nanotube, can also increase conventional carbon simultaneously Specific surface area improves the capacitor of active carbon, the characteristics such as bulk density;
(4) specific surface area of the activity Carbon composites reaches 2000m2/g-3500m2/ g, tap density reach 0.3g/ml-0.5g/ Ml, conductivity reach 0.3S/mm-0.8S/mm, quality specific capacitance > 251F/g.
It is specific as follows the present invention also provides a kind of method for preparing above-mentioned absorbent charcoal composite material:
Graphene or/and carbon nanotube are subjected to ultrasonic disperse processing into the water, obtain dispersion liquid;By active carbon particle It is added in dispersion liquid and is stirred to react, then wash, is dry, obtaining absorbent charcoal composite material.
Preferably, the dispersion concentration of the graphene or/and carbon nanotube in water is 0.1wt%-2wt%.
Preferably, the mass ratio of the active carbon and dispersion liquid is 1:10-1:25.
Preferably, the drying temperature is 60-270 DEG C.
The preparation process of the graphene is unlimited.As a kind of implementation, the concept of solid phase removing is applied to liquid phase, Selection graphite is raw material, carries out expansion pretreatment to graphite material.It is made of that is, being dipped into graphite intercalator and hydrogen peroxide Solution in, so that solvent molecule is intercalation into the interlayer of graphite, obtain compound between graphite layers, i.e. expansible graphite;Then, may be used Expanded graphite quickly heats under the protection of argon gas, and the solvent molecule of graphite layers is rapidly decomposed into vapor and carbon dioxide, Vapor and carbon dioxide volume sharply become larger expansion, this power is greater than the Van der Waals force of graphite layers, expand graphite layers It opens, obtains expanded graphite.Then, removing screening is carried out using ultrasonic disperse liquid phase stripping method, obtains graphene product.
The preparation method of the active carbon is unlimited.As a kind of implementation, be by timber, sawdust, tree root, fruit stone and The wood materials such as shell are made after being carbonized and being activated.The active carbon as obtained by coconut husk has high mechanical strength, hole Many advantages, such as structure prosperity, large specific surface area, so raw material of the preferred coconut husk as active carbon herein.
Charing is to thermally decompose wood materials, and complex chemical reaction occurs for wood materials in pyrolytic process. It can be generally divided into following four-stage with features, the carbonization process such as product is generated according to the temperature change in thermal decomposition process.
(1) drying stage
For the temperature in this stage at 20-150 DEG C, pyrolysis rate is very slow, mainly in wood materials contained humidity according to Heat by externally supplying is evaporated, and the chemical composition of wood materials has almost no change.
(2) pre- carbonization stage
The temperature in this stage is 50-275 DEG C, and wood materials pyrolysis is obvious, wood materials chemical composition Variation takes place, wherein unstable component, such as hemicellulose decompose and generate carbon dioxide, carbon monoxide and a small amount of acetic acid Substance.
The two above stage extraneous will supply heat to guarantee the rising of pyrolysis temperature, so also known as endothermic decomposition rank Section.
(3) carbonization stage
The temperature in this stage is 75-400 DEG C, and at this stage, wood materials are sharp thermally decomposed, and is generated big Decomposition product is measured, a large amount of acetic acid, methanol and wood tar, carbon dioxide in the gaseous product of generation are contained in the product liquid of generation Content gradually decreases, and the imflammable gas such as methane, ethylene gradually increase.This stage releases a large amount of reaction heat, so also known as For the exothermic reaction stage.
(4) calcination stage
The temperature in this stage is 450-500 DEG C, and by the calcining for externally supplying heat progress charcoal, discharge remains in wood Volatile materials in charcoal improves the fixation carbon content of charcoal, and it is seldom at this moment to generate product liquid.
It should be pointed out that the boundary in aforementioned four stage is difficult to clearly divide in actual carbonisation, due to carbonization device Each position received heat is different, and the thermal coefficient of wood materials is again smaller, and therefore, in equipment the location of wood materials are not no Together in addition bolt timber it is inside and outside, it is also possible to be in different pyrolysis phases.
Activation method includes physical activation method and chemical activation method.
Physical activation method is to activate the raw material after charing at high temperature with physically activated dose, and principle is by oxidation Carbon atom and form spatial joint clearance structure.Physically activated dose of generally vapor, carbon dioxide, air or their mixing synthesis Gas.The problems such as physical activation method is easy to operate, simple production process, avoids equipment corrosion and environmental pollution.It produces Come activated carbon product have it is free of cleaning, can be used directly, it is widely used the features such as.
Chemical activation method is to be mixed with dipping raw material and chemical reagent, the work carried out simultaneously with charing at a certain temperature Change method.Chemical activation method is with activation temperature is lower, active carbon acquisition rate is higher, spatial joint clearance structure is flourishing, adsorptivity Higher advantage.
Absorbent charcoal composite material of the invention can be used for the lead plaster cathode of lead carbon battery, that is, in the lead for preparing lead carbon battery In cream negative electrodes, the absorbent charcoal composite material is added in lead plaster, mixing paste is uniform, has the following beneficial effects:
(1) density of traditional active carbon or other charcoal class additives and lead powder density have biggish difference, in mixing paste It is difficult to for active carbon or other charcoal class additives being uniformly dispersed in the process.If by carbon nanotube or graphene separately as lead The charcoal class additive of carbon battery is easy to reunite due to its lighter weight, should not be also dispersed in lead plaster.The present invention uses Graphene or/and carbon nanotube are intercalated into active carbon and constitute composite material, quality, the accumulation for increasing conventional carbon are close Degree and specific surface area, i.e., absorbent charcoal composite material of the invention have biggish mass density and biggish particle size, institute To be easy to be uniformly dispersed when carrying out mixing paste with lead plaster.
(2) the charcoal class additive of traditional lead carbon battery has a single function, and adding technology process is complicated, such as traditional activity Charcoal is because the features such as its electric conductivity is poor, mechanical structure is weak also needs that the benefit of the highly conductive substance progress of such as carbon black functionally is added It fills.The present invention enters graphene or carbon nanotube intercalation among active carbon, and quality, the accumulation for not only increasing conventional carbon are close Degree and specific surface area also add the performance indicators such as electric conductivity, the specific capacitance of active carbon, therefore can less or even substitution charcoal The addition of black equal conductive agents, so as to further increase dispersing uniformity.
In conclusion the present invention is by the way that graphene or/and carbon nanotube to be combined in active carbon skeleton, constituting has surely The absorbent charcoal composite material for determining structure not only increases the mechanical structure stability of active carbon, also improves leading for active carbon Electrical property, while the specific surface area of active carbon is increased, improve the capacitor of active carbon, the characteristics such as bulk density.By the activity When Carbon composites are used for lead carbon battery, mechanical structure stability, the electric conductivity of cathode are not only contributed to, additionally it is possible to improve negative The mixing uniformity of pole and lead plaster effectively improves the overall performance of lead carbon battery.
Specific embodiment
Present invention is further described in detail with reference to embodiments, it should be pointed out that embodiment described below purport It is being convenient for the understanding of the present invention, and is not playing any restriction effect to it.
Embodiment 1:
A kind of absorbent charcoal composite material the preparation method is as follows:
(1) using coconut husk as raw material, coconut husk is carbonized and cocoanut active charcoal, the oxygen for being then 10mm with diameter are made after activation Change aluminium ball ball milling 12 hours, it is dry after ball milling, then handle with the sieve of 1000 mesh and pass through it is ultrasonic twice wash, obtain The uniform active carbon particle of grain;
(2) graphene by piece diameter less than 200um, which is added to the water, carries out ultrasonic disperse processing 2h, and obtaining graphene concentration is The dispersion liquid of 0.1wt%;
(3) active carbon particle that step (1) obtains is added in the dispersion liquid of step (2), wherein active carbon and dispersion The mass ratio of liquid is 1:25, is stirred to react in 60 DEG C of constant temperature, takes out after 5 hours, dry at 100 DEG C, then is put it into Sieving is handled in the sieve of 500 mesh, obtains absorbent charcoal composite material.
Absorbent charcoal composite material obtained above can be used for the cathode lead plaster additive of lead carbon battery.That is, preparing lead charcoal In the lead plaster negative electrodes of battery, the absorbent charcoal composite material is added in lead plaster, mixing paste divides absorbent charcoal composite material uniformly It is dispersed in lead plaster.
Embodiment 2:
A kind of absorbent charcoal composite material the preparation method is as follows:
(1) using coconut husk as raw material, coconut husk is carbonized and cocoanut active charcoal, the oxygen for being then 6mm with diameter are made after activation Change aluminium ball ball milling 12 hours, it is dry after ball milling, then handle with the sieve of 5000 mesh and pass through it is ultrasonic twice wash, obtain The uniform active carbon particle of grain;
(2) carbon nanotube by length less than 50um, which is added to the water, carries out ultrasonic disperse processing 2h, and it is dense to obtain carbon nanotube Degree is the dispersion liquid of 2wt%;
(3) active carbon particle that step (1) obtains is added in the dispersion liquid of step (2), wherein active carbon and dispersion The mass ratio of liquid is 1:10, is stirred to react in 100 DEG C of constant temperature, takes out after 5 hours, dry at 270 DEG C, then is put it into Sieving is handled in the sieve of 1000 mesh, obtains absorbent charcoal composite material.
Absorbent charcoal composite material obtained above can be used for the cathode lead plaster additive of lead carbon battery.That is, preparing lead charcoal In the lead plaster negative electrodes of battery, the absorbent charcoal composite material is added in lead plaster, mixing paste divides absorbent charcoal composite material uniformly It is dispersed in lead plaster.
Embodiment 3:
A kind of absorbent charcoal composite material the preparation method is as follows:
(1) using coconut husk as raw material, coconut husk is carbonized and cocoanut active charcoal, the oxygen for being then 6mm with diameter are made after activation Change aluminium ball ball milling 12 hours, it is dry after ball milling, then handle with the sieve of 5000 mesh and pass through it is ultrasonic twice wash, obtain The uniform active carbon particle of grain;
(2) carbon nanotube of the graphene by piece diameter less than 200um and length less than 50um, which is added to the water, surpasses
Sound decentralized processing 2h obtains graphene and carbon nanotube concentration as the dispersion liquid of 1wt%;
(3) active carbon particle that step (1) obtains is added in the dispersion liquid of step (2), wherein active carbon and dispersion The mass ratio of liquid is 1:20, is stirred to react in 100 DEG C of constant temperature, takes out after 5 hours, dry at 270 DEG C, then is put it into Sieving is handled in the sieve of 1000 mesh, obtains absorbent charcoal composite material.
Absorbent charcoal composite material obtained above can be used for the cathode lead plaster additive of lead carbon battery.That is, preparing lead charcoal In the lead plaster negative electrodes of battery, the absorbent charcoal composite material is added in lead plaster, mixing paste divides absorbent charcoal composite material uniformly It is dispersed in lead plaster.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention, Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.

Claims (7)

1. a kind of preparation method of absorbent charcoal composite material, it is characterized in that: graphene or/and carbon nanotube are carried out into the water Ultrasonic disperse processing, obtains dispersion liquid;Active carbon particle is added in dispersion liquid and is stirred to react, then washes, is dry, being lived Property carbon composite;
The piece diameter of the graphene is less than 200um, and the pipe range of carbon nanotube is less than 50um;
The absorbent charcoal composite material is using the absorbent charcoal material with open structure as basic framework, graphene or/and carbon nanometer Pipe is intercalated into the open structure of active carbon, and specific surface area reaches 2000m2/g-3500m2/ g, tap density reach 0.3g/ml- 0.5g/ml, conductivity reach 0.3S/mm-0.8S/mm, quality specific capacitance > 251F/g.
2. the preparation method of absorbent charcoal composite material as described in claim 1, it is characterized in that: the active carbon is living for coconut husk Property charcoal.
3. the preparation method of absorbent charcoal composite material as described in claim 1, it is characterized in that: the graphene and carbon nanometer The mass ratio of active carbon described in the quality sum of pipe is 0.01:1-0.5:1.
4. the preparation method of absorbent charcoal composite material as described in claim 1, it is characterized in that: the graphene or/and carbon The dispersion concentration of nanotube in water is 0.1wt%-2wt%.
5. the preparation method of absorbent charcoal composite material as described in claim 1, it is characterized in that: the drying temperature is 60- 270℃。
6. the preparation method of absorbent charcoal composite material as described in claim 1, it is characterized in that: the active carbon and dispersion liquid Mass ratio be 1:10-1:25.
7. a kind of lead carbon battery, in lead plaster negative plate preparation process, addition such as any power in claim 1 to 6 in lead plaster Benefit requires absorbent charcoal composite material obtained and mixing paste is uniform.
CN201610713156.3A 2016-08-23 2016-08-23 Absorbent charcoal composite material, preparation method and the lead carbon battery using the absorbent charcoal composite material Active CN106129368B (en)

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CN109309231B (en) * 2018-09-10 2021-10-29 安徽理士电源技术有限公司 Graphene composite slurry and preparation method thereof
CN110970603A (en) * 2018-09-30 2020-04-07 山东欧铂新材料有限公司 Multifunctional activated carbon composite material for negative electrode of lead-carbon battery, preparation method of multifunctional activated carbon composite material and lead-carbon battery
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