CN106856235A - Lead carbon superbattery negative material and preparation method thereof - Google Patents
Lead carbon superbattery negative material and preparation method thereof Download PDFInfo
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- CN106856235A CN106856235A CN201710019276.8A CN201710019276A CN106856235A CN 106856235 A CN106856235 A CN 106856235A CN 201710019276 A CN201710019276 A CN 201710019276A CN 106856235 A CN106856235 A CN 106856235A
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
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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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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 provides a kind of lead carbon superbattery negative material, and it is Graphene/Pb nano composite materials, after being mixed with graphite oxide solution by lead salt solution, through hydro-thermal reaction, then is formed by macroscopic body freeze-drying, firing；In the Graphene/Pb nano composite materials, lead accounts for 91%~99.5%, and Graphene accounts for 0.5~9%；The lead salt solution is dissolved in deionized water by soluble lead salt and is formulated, and the soluble lead salt is one or more in the nitrate containing lead element, acetate, carbonate, hydrochloride, sulfate and complex salt.The present invention also provides the preparation method of above-mentioned lead carbon superbattery negative material.Preparation method of the present invention has the advantages that efficiency high, environmental protection, homogeneity are high, and prepared Graphene/Pb nano composite materials homogeneity is good, and stability is high, and application prospect is extensive.
Description
Technical field
The present invention relates to super accumulator technical field, more particularly to a kind of lead carbon superbattery negative material and its preparation
Method.
Background technology
Lead-acid accumulator, has had more than the 150 years secondary cell of history as a kind of, because its technology maturation, low cost,
The advantages of security is good, is widely used in the fields such as start and stop, energy storage, communication, illumination, automobile, low-speed electronic car.2005-2009
Year Chinese plumbic acid battery industry average speed of growth reaches 30%, China be currently global maximum lead-acid storage battery production state with
Maximum lead-acid accumulator consumption state.
Under high rate partial state of charge circulation, negative pole plate surface can form lead sulfate crystal layer to traditional lead acid batteries, i.e.,
Sulfation, causes to reduce active material utilization reduction, and conductive capability declines, so that cell discharge performance declines, circulates the longevity
Life is reduced.
Lead carbon super accumulator concept is proposed by Australia Commonwealth Scientific and Industrial Research Organisation, carbon material is added to
The performance of super capacitor is played in negative plate, buffer is played a part of during high magnification charge/discharge, effectively protect negative pole
Plate, suppresses " sulfation " phenomenon, has opened the new chapter of lead-acid accumulator.But current grinding in super accumulator both at home and abroad
Some technologies and process difficulties are still suffered from hair, the large-scale application of super accumulator is limited.Number of patent application
201010543828.3 propose when positive and negative pole plate makes directly to active material in addition 5%~8% absorbent charcoal material or lead
Electro-graphitic, this technique improves super hybrid storage battery active material utilization and battery pack overall output power, but specific
Because lead powder is big with powdered carbon density difference in implementation, it is difficult to well mixed, while mixing charcoal pole plate has the hidden danger such as charcoal precipitation, easily
Cause inside battery micro-short circuit, battery security reduction.Patent application 201110008608.5 is proposed in super accumulator negative pole
Add activated carbon to add polyfluortetraethylene of binding element 0.2%~2.5% simultaneously in active material, strengthen active material adhesion.But
The addition of binding agent can improve the internal resistance of cell, while increasing and cream technique difficulty.In addition, patent application 201010216570.6 is public
The formula of another double property negative plate has been opened, on the basis of negative pole mixes 0.1%~5% conductive carbon material, liberation of hydrogen has been added
One or more combination in inhibitor, i.e. tin oxide, bismuth oxide or cerium oxide suppresses negative pole liberation of hydrogen problem.But a small amount of analysis
Hydrogen inhibitor is difficult to be well mixed by simple mechanical agitation and lead plaster, and it is miscellaneous to add substantial amounts of inhibitor to improve negative pole
Prime element content, is unfavorable for improving battery performance, also without the problem for fundamentally solving negative pole liberation of hydrogen.
Material prepared by the above method is as just the additive of negative plate, and one side effect is limited, be on the other hand
Additive is added on the basis of existing can increase battery holistic cost, be that industrialization process brings many difficulties.
The content of the invention
Defect it is an object of the invention to overcome prior art, there is provided a kind of lead carbon superbattery negative material and its system
Preparation Method.Lead carbon superbattery negative material of the present invention is Graphene/Pb nano composite materials, is that one kind can be while meet super
Electrode material in parallel in level capacitor and electrochmical power source, the generation of liberation of hydrogen situation is not had, is used directly for closing cream making electricity
Pond, without adding other inhibitor.And the preparation method of lead carbon superbattery negative material of the present invention, it is one brand-new
Green, economic, environmentally friendly negative material production line, many scientific workers are to the excellent of lead accumulator negative material before combining
Gesture, while having taken into account misgivings of the industrial circle on cost.
To achieve the above object, the present invention provides a kind of lead carbon superbattery negative material, and it is Graphene/Pb nanometers multiple
Condensation material, after being mixed with graphite oxide solution by lead salt solution, through hydro-thermal reaction, then by macroscopic body freeze-drying, firing
Into；
In the Graphene/Pb nano composite materials, lead accounts for 91%~99.5%, and Graphene accounts for 0.5~9%；
The lead salt solution is dissolved in deionized water by soluble lead salt and is formulated, and the soluble lead salt is containing lead element
One or more in nitrate, acetate, carbonate, hydrochloride, sulfate and complex salt.
The present invention also provides the preparation method of above-mentioned lead carbon superbattery negative material, comprises the following specific steps that：
1）Material prepares：By graphite oxide water dissolves, the graphite oxide solution of 0.5~10mg/ml is configured to；By dissoluble lead
Salt is dissolved in deionized water, and compound concentration is the lead salt solution of 0.01~2mol/l；
2）Mixed material：It is ultrasonically treated to graphite oxide solution, it is allowed to be dispersed into homogeneous graphene oxide colloidal solution, then to
Above-mentioned lead salt solution, 5~30min of ultrasonic vibration is wherein added to pour into autoclave；
3）Hydro-thermal reaction：Autoclave is fixed, is subsequently placed in constant temperature explosion-proof tank, 25~30h of hydro-thermal reaction；
4）Dried process：The macroscopic body of preparation is taken out, is placed in atmosphere baking oven, dried to micro- moisture state, be then placed in
In vacuum freeze-drying machine, 48~72h of freeze-drying time；
5）Firing is processed：By lyophilized crushing material, then fired in atmosphere furnace, sintering procedure is divided into two stages；First
Stage, programming rate is 10~20 DEG C/min, is warming up to 400~600 DEG C, 2~3h of temperature；Second stage, programming rate
It is 2~5 DEG C/min, is warming up to 700~900 DEG C, is incubated 2~3h.
Preferably, the step 1）In, soluble lead salt is the nitrate containing lead element, acetate, carbonate, hydrochloric acid
One or more in salt, sulfate and complex salt.
Preferably, the step 1）In, the concentration of graphite oxide solution is 0.5~3mg/ml.
Preferably, the step 3）In, the temperature control of constant temperature explosion-proof tank is at 220~300 DEG C.
Preferably, the final Graphene/Pb nano composite materials for preparing, in Internet flake graphite alkene outer surface and internal layer
In be uniformly distributed nanoscale Pb, average grain diameter is 0.2~100 μm.
The advantages of the present invention are：A kind of lead carbon superbattery negative material and preparation method thereof is provided.
Lead carbon superbattery negative material of the present invention is Graphene/Pb nano composite materials, is that one kind can be while meet super capacitor
Electrode material in parallel in device and electrochmical power source, the generation of liberation of hydrogen situation is not had, is used directly for closing cream making battery, without
Need to add other inhibitor.And the preparation method of lead carbon superbattery negative material of the present invention, it is brand-new green, a warp
Ji, environmentally friendly negative material production line, before combining many scientific workers to the advantage of lead accumulator negative material, while
Misgivings of the industrial circle on cost are taken into account.
Specifically, the present invention can simultaneously reach following requirement：
The electric conductivity of GND is effectively improved, internal resistance is reduced；
Lead carbon superbattery negative material of the present invention provides certain electro-chemical activity capacity, increase moment high-power charging/put
The ability of electricity；
Lead carbon superbattery negative material of the present invention has complicated network lamellar carbon structure, can allow and be electrolysed liquid pump to pole plate
Inside, makes internal active material fully react, and improves the utilization rate of active material, increases battery whole volume；
Lead carbon superbattery negative material of the present invention is the key and compound of lead and Graphene, is ensureing the double capacitance characteristics of carbon material
While, the uniformity of electrochemical potentials is also ensured, therefore avoid liberation of hydrogen problem；
Lead carbon superbattery negative material of the present invention is the key and compound of lead and Graphene, during repeated charge, no
Can be separated out because of Volume Changes, therefore decarburization problem is avoided from root.
Lead carbon superbattery negative material of the present invention is the key and compound of lead and Graphene, breaches other researchers and exists
The way of carbon material is originally added in negative plate, it is to avoid increase cost.
In order to reach above-mentioned requirements simultaneously, the present invention devises preferable material structure.Using the water-soluble of graphene oxide
Property and electrostatic coupling effect, allow it is nonmetallic is combined with metal ion, formed uniformly " peanut structure ", then by firing, allow
Graphene oxide reduction becomes the good Graphene of electric conductivity, while a large amount of nanoscale lead are coated in Internet laminated structure,
And be separated from each other, so similar to numerous small cage is formed in spatial dimension, numerous lead particle is wrapped in graphite
In the grid of alkene.
Unique structure and performance of lead carbon composite are the reason for ensureing superbattery performance.Specifically, it is combined
Material has good electric conductivity, electric double layer capacitance and extremely low hydrogen-evolution overpotential.Described extremely low hydrogen-evolution overpotential, refers to -1.2
Under (being directed to reversible hydrogen electrode) V current potentials, its liberation of hydrogen electric current is in below 1mA/mg.
In structure, the composite is bonded with nanometer lead by porous carbon materials and formed.The wherein weight of nanometer lead-containing materials
Amount is than being 90~95%.By structural analysis, described lead-containing materials have the simple substance and oxide of lead, and wherein lead simple substance is occupied
More than 90%.After being made battery and charging, the leaded material in electrode can change, multiple as the lead carbon with negative electrode active
Condensation material.
After above two raw material is compound, obtains conductive Carbon Materials and be coated on the oxidation of conductive charcoal material surface and interlayer
Lead and lead, wherein lead account for more than the 90% of composite gross weight of the present invention.
The lead carbon composite obtained by above-mentioned technique, in the negative pole as additive addition lead-acid battery, and existing skill
Art is compared, with advantages below：
1st, beneficial to mixing and cream.Pb/C composite proportions are further improved, when solving traditional handicraft powdered carbon and mixing with lead powder
Because the big caused mixing problem of non-uniform of difference of specific gravity, and cream process are simple to operation.
2nd, liberation of hydrogen is suppressed.It is bonded with Graphene by Pb and is linked, be modified conductive Carbon Materials, it is to avoid lead paste formula introducing
Other impurities metal oxide inhibitor, equally serves good inhibiting effect to negative plate hydrogen evolution phenomenon.
3rd, carburizing is prevented.In traditional carbon dope technique, conductive Carbon Materials and making cathode lead plaster institute with high-specific surface area
There is significantly surface property difference between lead powder surface, mixed Interface adhesive strength is very poor, in charge and discharge cycles
During, conductive Carbon Materials are easy to separate out, and cause negative electrode active material to depart from too early, and the life-span is substantially reduced.And Pb/C is compound
Material, as conductive Carbon Materials pore surface PbO is electrochemically transformed, is formed with Pb in lead plaster and handed over during battery charging/discharging
It is coupled structure, so as to conductive Carbon Materials are pinned inside lead plaster, fundamentally solve carbon and separate out problem.
4th, capacitance characteristic.Because Pb/C composites and lead plaster are combined closely, hole is more, and internal resistance is smaller, and battery charges
Ability to accept, heavy-current discharge performance etc. are significantly better than the dual pole plate that commonsense method is made.For hybrid vehicle, use
Life-span improves 2~3 times.
The present invention also has following features：
1st, lamellar Graphene plays conductive network effect, greatly improves pole plate monolithic conductive；And in the aspect of surrounding and watching
Separate the reunion of Pb, it is thinner to be allowed to particle, dispersion evenly, while allow Pb to be tightly dispersed in lamellar decker sandwich, significantly
The utilization ratio of lead is improved, to weaken negative pole sulfation problem.
2nd, negative plate directly prepares negative electrode material lead by the method for chemical synthesis, gets around traditional into link, subtracts
Few energy consumption, and environmental protection.
3rd, cell negative plate electrode material is the composite of Graphene and lead, on the one hand, the conductive mesh that Graphene is formed
Network improves the monolithic conductive of pole plate, while netted Graphene increased the sponginess of pole plate, the carbon of layer structure is played
The effect of pump, allows the electrolyte in the external world more to enter pole plate internal layer, so that the lead of pole plate internal layer is fully reacted, improves
Plate active material utilization rate.
4th, Graphene/Pb composites are composited by hydro-thermal using graphite oxide and lead salt, are not simple machines
Tool mixes, and the two-phase of this composite has bonding action between nonmetal graphite alkene and metallic lead, therefore is evenly distributed,
It is firmly combined with, and lead particle is in nanometer level, is distributed between the surface of mesh material and interlayer.
Brief description of the drawings
Fig. 1 schemes for the SEM of Graphene of the invention/Pb nano composite materials；
Fig. 2 schemes for the TEM of Graphene of the invention/Pb nano composite materials.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiment of the invention is further described.Following examples are only
For clearly illustrating technical scheme, and can not be limited the scope of the invention with this.
The present invention provides a kind of lead carbon superbattery negative material, and it is Graphene/Pb nano composite materials, molten by lead salt
After liquid mixes with graphite oxide solution, through hydro-thermal reaction, then formed by macroscopic body freeze-drying, firing；
In the Graphene/Pb nano composite materials, lead accounts for 91%~99.5%, and Graphene accounts for 0.5~9%；
The lead salt solution is dissolved in deionized water by soluble lead salt and is formulated, and the soluble lead salt is containing lead element
One or more in nitrate, acetate, carbonate, hydrochloride, sulfate and complex salt.
The present invention also provides the preparation method of above-mentioned lead carbon superbattery negative material, comprises the following specific steps that：
1）Material prepares：By graphite oxide water dissolves, 0.5~10mg/ml is configured to（Preferably 0.5~3mg/ml）Oxidation
Graphite solution；Soluble lead salt is dissolved in deionized water, compound concentration is the lead salt solution of 0.01~2mol/l；Dissoluble lead
Salt is one or more in the nitrate containing lead element, acetate, carbonate, hydrochloride, sulfate and complex salt；
2）Mixed material：It is ultrasonically treated to graphite oxide solution, it is allowed to be dispersed into homogeneous graphene oxide colloidal solution, then to
Above-mentioned lead salt solution, 5~30min of ultrasonic vibration is wherein added to pour into autoclave；
3）Hydro-thermal reaction：Autoclave is fixed, is subsequently placed in constant temperature explosion-proof tank, the temperature control of constant temperature explosion-proof tank exists
220~300 DEG C, 25~30h of hydro-thermal reaction；
4）Dried process：The macroscopic body of preparation is taken out, is placed in atmosphere baking oven, dried to micro- moisture state, be then placed in
In vacuum freeze-drying machine, 48~72h of freeze-drying time；
5）Firing is processed：By lyophilized crushing material, then fired in atmosphere furnace, sintering procedure is divided into two stages；First
Stage, programming rate is 10~20 DEG C/min, is warming up to 400~600 DEG C, 2~3h of temperature；Second stage, programming rate
It is 2~5 DEG C/min, is warming up to 700~900 DEG C, is incubated 2~3h；
Final Graphene/Pb the nano composite materials for preparing, are uniformly distributed in Internet flake graphite alkene outer surface and internal layer
Nanoscale Pb, average grain diameter is 0.2~100 μm.
The SEM figures of Graphene of the invention/Pb nano composite materials are as shown in Figure 1；Graphene/Pb nanometers of the invention multiple
The TEM figures of condensation material are as shown in Figure 2.
The technical scheme of present invention specific implementation is as follows：
Embodiment 1
Configuration lead acetate water solution, concentration is 0.1M, and it is the graphite oxide solution of 2ml/mg to add concentration.Lead acetate water solution with
Graphene oxide solution volume ratio is 90:10,25~30h of hydro-thermal, dry, in inert atmosphere, atmosphere under 80 DEG C of condition of nitrogen gas
It is heat-treated in stove, obtains lead/carbon composite.
Embodiment 2
The configuration plumbi nitras aqueous solution, concentration is 0.1M, and it is the graphite oxide solution of 2ml/mg to add concentration.Lead acetate water solution with
Graphene oxide solution volume ratio is 90:10,25~30h of hydro-thermal, dry, in inert atmosphere, atmosphere under 80 DEG C of condition of nitrogen gas
It is heat-treated in stove, obtains lead/carbon composite.
Embodiment 3
Configuration lead acetate water solution, concentration is 0.1M, and it is the graphite oxide solution of 2ml/mg to add concentration.Lead acetate water solution with
Graphene oxide solution volume ratio is 80:20,25~30h of hydro-thermal, dry, in inert atmosphere, atmosphere under 80 DEG C of condition of nitrogen gas
It is heat-treated in stove, obtains lead/carbon composite.
Embodiment 4
The configuration plumbi nitras aqueous solution, concentration is 0.1M, and it is the graphite oxide solution of 2ml/mg to add concentration.Lead acetate water solution with
Graphene oxide solution volume ratio is 80:20,25~30h of hydro-thermal, dry, in inert atmosphere, atmosphere under 80 DEG C of condition of nitrogen gas
It is heat-treated in stove, obtains lead/carbon composite.
Then, the Pb/C composites that will be prepared, make according to battery and are formulated, and carry out lead plaster and system.The lead that will be obtained again
Cream is coated to negative electrode grid, manufactures super accumulator negative plate.
Test result：
The XRD diffracting diagrams of material of the present invention reveal the characteristic peaks of amorphous carbon, lead oxide and lead-containing compounds, illustrate system
Standby material is that grapheme material is combined into entirety with oxidation lead material.
Modified carbon material is in acid accumulator negative pole lead operating voltage range（- 0.4V~-0.9V vs.SCE）Inside substantially not
Liberation of hydrogen, illustrates that lead carbon composite liberation of hydrogen problem of the present invention is significantly improved.
By the method for embodiment 3,7Ah is respectively prepared, after the 12V lead carbon batteries of 9Ah, its cyclicity is tested according to national standard
Can, lead carbon battery shows the cycle performance more much better than conventional lead acid battery.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, on the premise of the technology of the present invention principle is not departed from, some improvements and modifications can also be made, these improvements and modifications
Also should be regarded as protection scope of the present invention.
Claims (6)
1. lead carbon superbattery negative material, it is characterised in that it is Graphene/Pb nano composite materials, by lead salt solution with
After graphite oxide solution mixing, through hydro-thermal reaction, then formed by macroscopic body freeze-drying, firing；
In the Graphene/Pb nano composite materials, lead accounts for 91%~99.5%, and Graphene accounts for 0.5~9%；
The lead salt solution is dissolved in deionized water by soluble lead salt and is formulated, and the soluble lead salt is containing lead element
One or more in nitrate, acetate, carbonate, hydrochloride, sulfate and complex salt.
2. the preparation method of lead carbon superbattery negative material described in claim 1, it is characterised in that including following specific step
Suddenly：
1）Material prepares：By graphite oxide water dissolves, the graphite oxide solution of 0.5~10mg/ml is configured to；By dissoluble lead
Salt is dissolved in deionized water, and compound concentration is the lead salt solution of 0.01~2mol/l；
2）Mixed material：It is ultrasonically treated to graphite oxide solution, it is allowed to be dispersed into homogeneous graphene oxide colloidal solution, then to
Above-mentioned lead salt solution, 5~30min of ultrasonic vibration is wherein added to pour into autoclave；
3）Hydro-thermal reaction：Autoclave is fixed, is subsequently placed in constant temperature explosion-proof tank, 25~30h of hydro-thermal reaction；
4）Dried process：The macroscopic body of preparation is taken out, is placed in atmosphere baking oven, dried to micro- moisture state, be then placed in
In vacuum freeze-drying machine, 48~72h of freeze-drying time；
5）Firing is processed：By lyophilized crushing material, then fired in atmosphere furnace, sintering procedure is divided into two stages；First
Stage, programming rate is 10~20 DEG C/min, is warming up to 400~600 DEG C, 2~3h of temperature；Second stage, programming rate
It is 2~5 DEG C/min, is warming up to 700~900 DEG C, is incubated 2~3h.
3. the preparation method of lead carbon superbattery negative material according to claim 2, it is characterised in that the step 1）
In, soluble lead salt is the one kind in the nitrate containing lead element, acetate, carbonate, hydrochloride, sulfate and complex salt
Or it is several.
4. the preparation method of lead carbon superbattery negative material according to claim 3, it is characterised in that the step 1）
In, the concentration of graphite oxide solution is 0.5~3mg/ml.
5. the preparation method of lead carbon superbattery negative material according to claim 4, it is characterised in that the step 3）
In, the temperature control of constant temperature explosion-proof tank is at 220~300 DEG C.
6. the preparation method of lead carbon superbattery negative material according to claim 5, it is characterised in that the final stone for preparing
Black alkene/Pb nano composite materials, nanoscale Pb, average grain diameter are uniformly distributed in Internet flake graphite alkene outer surface and internal layer
It is 0.2~100 μm.
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| CN107611446A (en) * | 2017-09-20 | 2018-01-19 | 厦门稀土材料研究所 | A kind of liberation of hydrogen inhibitor, preparation method and applications |
| CN108134092A (en) * | 2017-12-19 | 2018-06-08 | 中南大学 | A kind of nanometer of lead/carbon composite and preparation method thereof |
| CN109841798A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of lead carbon battery cathode and its preparation and application |
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| CN109841798A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of lead carbon battery cathode and its preparation and application |
| CN109841833A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of lead carbon battery cathode and its preparation and application |
| CN108134092A (en) * | 2017-12-19 | 2018-06-08 | 中南大学 | A kind of nanometer of lead/carbon composite and preparation method thereof |
| CN108134092B (en) * | 2017-12-19 | 2020-06-16 | 中南大学 | Nano lead/carbon composite material and preparation method thereof |
| CN109980184A (en) * | 2017-12-28 | 2019-07-05 | 刘志勇 | A kind of preparation method of the double graphene negative plates of super lead acid storage battery |
| CN112864391A (en) * | 2021-01-27 | 2021-05-28 | 华侨大学 | Preparation method and application of lead/reduced graphene oxide nanocomposite |
| CN112864391B (en) * | 2021-01-27 | 2022-05-03 | 华侨大学 | Preparation method and application of lead/reduced graphene oxide nanocomposite |
| CN112928261A (en) * | 2021-02-24 | 2021-06-08 | 超威电源集团有限公司 | Lead powder with lead oxide graphene core-shell structure and preparation method thereof |
| CN113903915A (en) * | 2021-09-14 | 2022-01-07 | 浙江大学 | Preparation method of graphene-coated porous lead oxide-lead sulfide composite material |
| CN113903915B (en) * | 2021-09-14 | 2023-05-09 | 浙江大学 | Preparation method of graphene-coated porous lead oxide-lead sulfide composite material |
| CN117613250A (en) * | 2024-01-24 | 2024-02-27 | 帕瓦(长沙)新能源科技有限公司 | Three-dimensional conductive lead-carbon composite material, preparation method thereof, negative electrode and lead-acid battery |
| CN117613250B (en) * | 2024-01-24 | 2024-04-19 | 帕瓦(长沙)新能源科技有限公司 | Three-dimensional conductive lead-carbon composite material, preparation method thereof, negative electrode and lead-acid battery |
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