CN109841833A - A kind of lead carbon battery cathode and its preparation and application - Google Patents
A kind of lead carbon battery cathode and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of lead carbon battery cathode, the modified carbon fiber containing 0.1~50wt% in cathode, the modified carbon fiber is by first activating carbon fiber, then is poisoned and obtained；Not only reduce the cost of lead carbon battery, conductive network structure in negative plate, reduce the internal resistance of cell, effectively inhibit the sulfation of battery, reduce the water loss during lead carbon battery cycle life, overpotential of hydrogen evolution is improved, lead carbon battery charge and discharge circulation life (HRPSOC) under prolongation nuclear power state enhances battery charge acceptance and cold starting performance.
Description
Technical field
The present invention relates to field of electrochemical power source, in particular to a kind of lead carbon battery cathode.
Background technique
Lead carbon battery is a kind of novel high-power for mutually merging lead-acid accumulator with the superiority of asymmetric capacitor
The superbattery technology of density can play the energy advantage of lead-acid battery and play super capacitor instantaneous power and big
The advantages of capacity charges, becomes the development priority of international new energy energy storage industry, this battery adds in acid accumulator negative pole lead
Add active charcoal class material as charge buffer material, Carbon materials have the electric double layer capacitance characteristic of electrostatic charge storage release, energy
Guarantee that battery can be completed in a relatively short time charging in a large amount of charges of moment aggregating storing, can satisfy under high current density
Prolonged stable discharging better adapts to the demand for development of new-energy automobile or electric vehicle.The big electricity of lead-acid accumulator simultaneously
Serious sulfation can occur for positive and negative anodes when banishing electricity, i.e., generate the lead sulfate big compared with multiple grain in positive and negative anodes active material and exist
Be difficult to be converted to positive and negative anodes active material when charging, the bulky grain lead sulfate of this reunion can make accumulator capacity significantly under
Drop severely impacts the service life of lead-acid accumulator, and the Carbon materials with high electrical conductivity are in the negative active material
It is capable of forming conductive network, inhibits high current density to the impact of battery and the formation of sulfate, therefore study and prepare
The Carbon materials of excellent properties are the most important things.
Pennsylvania, America Axion Power company is first by high-specific surface area carbons material (such as active carbon, activity
Carbon fibe, carbon aerogels or carbon nanotube etc.) incorporation negative electrode active material in improve active material utilization, L.T in 2006
Doctor Lam describes super accumulator and is applied to micro- mix in partial state of charge heavy-current discharge performance and by super accumulator
The progress of electric vehicle is mixed in, and in application in 2007 " cathode for energy storage device " and " hybrid accumulator machine
Two patents of device manufacturing method "；On January 15th, 2008, Japan researcher passed through superbattery applied to hybrid electric vehicle
100000 miles of (about 160000km) life tests, battery condition are still good；India researcher Saravanan in 2012 et al. is delivered
The research achievement of Double-pole lug superbattery, the cycle life of discharge power and partial state of charge is significantly as the result is shown for this
It improves.Although domestic many enterprises, colleges and universities and institute (south all power supply, holy positive share, Harbin Institute of Technology etc.) all exist
The technical research work of lead carbon battery is carried out, the research direction of lead carbon battery technology is also more at present, is mainly reflected in lead carbon electricity
Pool structure improves (internal-mixing, interior and formula, full carbon are born board-like etc.), Carbon materials are modified etc., but most importantly finds optimal
Carbon materials are able to solve cathode liberation of hydrogen water loss problem, this is also the master for restricting lead carbon battery and applying and promote in new energy field
Factor is wanted, therefore the patent is the possible using another technology is provided of lead carbon battery in Carbon materials linguistic term, is anticipated
Justice is great.
Summary of the invention
It is an object of the invention to overcome above-mentioned technological deficiency, a kind of preparation side of lead carbon battery modified carbon fiber is provided
The preparation method of method and cathode lead plaster, using modified carbon fiber instead of in traditional lead acid batteries polyester fiber and carbon black or
Acetylene black-materials.
In order to achieve the above objectives, the specific technical solution that the present invention uses is as follows:
A kind of lead carbon battery cathode, cathode include lead material, the modified carbon fiber containing 0.1~50wt% in cathode, institute
The modified carbon fiber stated is by first activating carbon fiber, then is poisoned and obtained；Preferably modified carbon fiber content is
0.5~5wt%, 1~3wt% of preferred modified carbon fiber content；
Activation is that carbon fiber is placed in CO230min~for 24 hours is roasted in gas stove at 600~900 DEG C；Poison is that will live
Change carbon fiber uniformly to mix with liberation of hydrogen inhibitor, in an inert atmosphere the processing 10min~for 24 hours at 100~500 DEG C；
Wherein, liberation of hydrogen inhibitor is to contain one of metallic lead, tin, cerium, indium, bismuth, the aqueous solution of soluble-salt of samarium
Or two kinds or more, soluble-salt is one of nitrate, acetate, acetate or two kinds or more, and concentration is 0.1wt%~right
Answer the saturated concentration of metal soluble-salt；
Inert atmosphere is one of nitrogen, argon gas, ammonia or two kinds or more.
The cathode is made by the steps,
(1) take 100 mass parts of lead powder, barium sulfate and lignin mixture as additive 0.1-10 mass parts, modified carbon fiber
It ties up 0.1~50 mass parts and stirs dry-mixed 3~5min, mix well each component, obtain mixed powder；Barium sulfate in additive
It is 1:100~100:1 with lignin mixing mass ratio.
(2) 10~21 mass parts deionized waters are added in mixed powder, stirs 3~6 minutes, is then slowly added into density
1.1~1.4 g/cm34~100 mass parts sulfuric acid be uniformly mixing to obtain cathode lead plaster；
(3) lead plaster is scratched onto grid, it is cured to be dried to obtain lead carbon battery negative electrode tab；Active material is thick in negative electrode tab
Degree is 0.1~10mm；Solidification temperature is 10~100 DEG C, and relative humidity is 10~100%, curing time 1-50h；Dry temperature
Degree is 10~200 DEG C, and relative humidity is 0~80%, and drying time is 1~50h.
It is applied in lead carbon battery as cathode.
It is applied to internal hybrid lead carbon battery as cathode, is more preferably used for start-stop or energy storage internal hybrid lead carbon battery.
Inventive technique scheme bring beneficial effect
The cost for not only reducing lead carbon battery, the conductive network structure in negative plate reduce the internal resistance of cell, effectively press down
The sulfation for having made battery reduces the water loss during lead carbon battery cycle life, improves overpotential of hydrogen evolution, extension
Lead carbon battery charge and discharge circulation life (HRPSOC) under pyrene electricity condition enhances battery charge acceptance and cold cranking capacity
Energy.
(1) a kind of Carbon materials method of modifying is provided, this method can be applied to various Carbon materials (graphite, graphite
Alkene, carbon nanotube, lignin etc.).
(2) polyester fiber and the carbon materials such as carbon black or acetylene black in modified carbon fiber substitution traditional lead acid batteries, is used
In lead carbon battery, modified carbon fiber can effectively inhibit liberation of hydrogen side reaction, improve the charge and discharge under high current density
Performance, so as to improve the service life of lead carbon battery significantly.
(3) carbon material for effectively having evaded large specific surface area for modified carbon fiber in lead carbon battery mixes not with lead powder
Uniformity problem, while being fully able to solve lead plaster conductivity problems.
Detailed description of the invention
The LSV curve of Fig. 1 difference modified carbon fiber additive amount negative plate；
The CV curve of Fig. 2 difference modified carbon fiber additive amount negative plate.
Specific embodiment
Embodiment 1
10g carbon fiber is put into CO2It is burnt to 6h for 800 DEG C in gas stove；Carbon fiber after activation and 0.2g plumbi nitras are mixed again
It closes uniformly, then is poisoned processing 1h under inert atmosphere in 300 DEG C, obtain poisoning carbon fiber.Weigh lead powder 100g, additive (sulphur
Sour barium 1.2g, lignin 0.2g), modified carbon fiber 0.5g pour into paste mixing machine container dry-mixed 5 minutes, mix well each component,
Obtain mixture.10g deionized water is added in mixed powder, stirs 5 minutes, is then slowly added into density 1.2g/cm3's
10g sulfuric acid is uniformly mixing to obtain cathode lead plaster.Obtained lead carbon battery cathode lead plaster is directly coated on negative electrode grid, is carried out
It is put into controlled humidity high-low temperature chamber after rolling and leaching acid processing and carries out curing and drying program, under the conditions of 45 DEG C of relative humidity 95%
Solidify 36h, 85 DEG C of dry 9h obtain lead carbon battery negative plate.Using the lead carbon battery negative plate of preparation as working electrode, pass
The lead-acid battery positive plate of system is made to be saturated mercuric sulfate electrode to electrode and make reference electrode, three-electrode system is formed, to lead carbon battery
Negative plate carries out Electrochemical Characterization.The potential window of linear scan polarization curve is open circuit potential to -1.5V；Cyclic voltammetric
Potential window is 0 to -1.5V.Linear polarization and cyclic voltammetry result difference are as depicted in figs. 1 and 2.It is unmodified with adding
Carbon fiber negative plate and traditional lead acid batteries cathode are compared, and the lead carbon electricity of 0.5g modified carbon fiber is added in 100g lead powder
Pond cathode has lower liberation of hydrogen electric current.
Embodiment 2
10g carbon fiber is put into CO2It is burnt to 6h for 800 DEG C in gas stove；Carbon fiber after activation and 0.2g plumbi nitras are mixed again
It closes uniformly, then is poisoned processing 1h under inert atmosphere in 300 DEG C, obtain poisoning carbon fiber.Weigh lead powder 100g, additive (sulphur
Sour barium 1.2g, lignin 0.2g), modified carbon fiber 1.0g pour into paste mixing machine container dry-mixed 5 minutes, mix well each component,
Obtain mixture.10g deionized water is added in mixed powder, stirs 5 minutes, is then slowly added into density 1.2g/cm3's
10g sulfuric acid is uniformly mixing to obtain cathode lead plaster.Obtained lead carbon battery cathode lead plaster is directly coated on negative electrode grid, is carried out
It is put into controlled humidity high-low temperature chamber after rolling and leaching acid processing and carries out curing and drying program, under the conditions of 45 DEG C of relative humidity 95%
Solidify 36h, 85 DEG C of dry 9h obtain lead carbon battery negative plate.Using the lead carbon battery negative plate of preparation as working electrode, pass
The lead-acid battery positive plate of system is made to be saturated mercuric sulfate electrode to electrode and make reference electrode, three-electrode system is formed, to lead carbon battery
Negative plate carries out Electrochemical Characterization.The potential window of linear scan polarization curve is open circuit potential to -1.5V；Cyclic voltammetric
Potential window is 0 to -1.5V.Linear polarization and cyclic voltammetry result difference are as depicted in figs. 1 and 2.It is unmodified with adding
Carbon fiber negative plate and traditional lead acid batteries cathode are compared, and the lead carbon electricity of 1.0g modified carbon fiber is added in 100g lead powder
Pond cathode has lower liberation of hydrogen electric current.It is compared with cathode prepared by embodiment 1,3,4, cathode prepared by the present embodiment is living
Property highest, liberation of hydrogen electric current is minimum.
Embodiment 3
10g carbon fiber is put into CO2It is burnt to 6h for 800 DEG C in gas stove；Carbon fiber after activation and 0.2g plumbi nitras are mixed again
It closes uniformly, then is poisoned processing 1h under inert atmosphere in 300 DEG C, obtain poisoning carbon fiber.Weigh lead powder 100g, additive (sulphur
Sour barium 1.2g, lignin 0.2g), modified carbon fiber 1.5g pour into paste mixing machine container dry-mixed 5 minutes, mix well each component,
Obtain mixture.10g deionized water is added in mixed powder, stirs 5 minutes, is then slowly added into density 1.2g/cm3's
10g sulfuric acid is uniformly mixing to obtain cathode lead plaster.Obtained lead carbon battery cathode lead plaster is directly coated on negative electrode grid, is carried out
It is put into controlled humidity high-low temperature chamber after rolling and leaching acid processing and carries out curing and drying program, under the conditions of 45 DEG C of relative humidity 95%
Solidify 36h, 85 DEG C of dry 9h obtain lead carbon battery negative plate.Using the lead carbon battery negative plate of preparation as working electrode, pass
The lead-acid battery positive plate of system is made to be saturated mercuric sulfate electrode to electrode and make reference electrode, three-electrode system is formed, to lead carbon battery
Negative plate carries out Electrochemical Characterization.The potential window of linear scan polarization curve is open circuit potential to -1.5V；Cyclic voltammetric
Potential window is 0 to -1.5V.Linear polarization and cyclic voltammetry result difference are as depicted in figs. 1 and 2.It is unmodified with adding
Carbon fiber negative plate and traditional lead acid batteries cathode are compared, and the lead of 1.5g addition modified carbon fiber is added in 100g lead powder
Carbon battery cathode has lower liberation of hydrogen electric current.
Embodiment 4
10g carbon fiber is put into CO2It is burnt to 6h for 800 DEG C in gas stove；Carbon fiber after activation and 0.2g plumbi nitras are mixed again
It closes uniformly, then is poisoned processing 1h under inert atmosphere in 300 DEG C, obtain poisoning carbon fiber.Weigh lead powder 100g, additive (sulphur
Sour barium 1.2g, lignin 0.2g), modified carbon fiber 2.0g pour into paste mixing machine container dry-mixed 5 minutes, mix well each component,
Obtain mixture.10g deionized water is added in mixed powder, stirs 5 minutes, is then slowly added into density 1.2g/cm3's
10g sulfuric acid is uniformly mixing to obtain cathode lead plaster.Obtained lead carbon battery cathode lead plaster is directly coated on negative electrode grid, is carried out
It is put into controlled humidity high-low temperature chamber after rolling and leaching acid processing and carries out curing and drying program, under the conditions of 45 DEG C of relative humidity 95%
Solidify 36h, 85 DEG C of dry 9h obtain lead carbon battery negative plate.Using the lead carbon battery negative plate of preparation as working electrode, pass
The lead-acid battery positive plate of system is made to be saturated mercuric sulfate electrode to electrode and make reference electrode, three-electrode system is formed, to lead carbon battery
Negative plate carries out Electrochemical Characterization.The potential window of linear scan polarization curve is open circuit potential to -1.5V；Cyclic voltammetric
Potential window is 0 to -1.5V.Linear polarization and cyclic voltammetry result difference are as depicted in figs. 1 and 2.It is unmodified with adding
Carbon fiber negative plate and traditional lead acid batteries cathode are compared, and the lead carbon electricity of 0.5g modified carbon fiber is added in 100g lead powder
Pond cathode has lower liberation of hydrogen electric current.
Embodiment 5
30g carbon fiber is put into CO2It is burnt to 6h for 800 DEG C in gas stove；Carbon fiber is mixed with 1g plumbi nitras after activating again
Uniformly, then poisoned processing 1h under inert atmosphere in 300 DEG C, obtain poisoning carbon fiber.Weigh lead powder 500g, additive (sulfuric acid
Barium 6g, lignin 1g), modified carbon fiber 10g pour into paste mixing machine container dry-mixed 5 minutes, mix well each component, mixed
Object.10g deionized water is added in mixed powder, stirs 5 minutes, is then slowly added into density 1.2g/cm310g sulfuric acid stir
It mixes and uniformly obtains cathode lead plaster.Obtained lead carbon battery cathode lead plaster is directly coated on negative electrode grid, is rolled and is drenched
It is put into progress curing and drying program in controlled humidity high-low temperature chamber after acid processing, solidifies 36h under the conditions of 45 DEG C of relative humidity 95%,
85 DEG C of dry 9h, obtain lead carbon battery negative plate.Using lead carbon battery negative plate, the plumbic acid of the three above-mentioned preparations of positive two negative structure
It is 4.4Ah rich solution internal hybrid lead carbon battery that battery positive plate and PE diaphragm, which are assembled into rated capacity,.Using SBA S0101-2014
Method as defined in " start-stop vehicle lead-acid accumulator " standard carries out cycle life survey to the rich solution internal hybrid lead carbon battery of preparation
Examination.The result shows that rich solution lead carbon battery cycle life prepared by the present embodiment reaches 54000 times, it is that comparative example 2 is made
3 times of standby lead-acid battery service life.
Embodiment 6
10g carbon fiber is put into CO2It is burnt to 6h for 800 DEG C in gas stove；Carbon fiber after activation and 0.2g plumbi nitras are mixed again
It closes uniformly, then is poisoned processing 1h under inert atmosphere in 300 DEG C, obtain poisoning carbon fiber.Weigh lead powder 100g, additive (sulphur
Sour barium 1.2g, lignin 0.2g), modified carbon fiber 2.0g pour into paste mixing machine container dry-mixed 5 minutes, mix well each component,
Obtain mixture.10g deionized water is added in mixed powder, stirs 5 minutes, is then slowly added into density 1.2g/cm3's
10g sulfuric acid is uniformly mixing to obtain cathode lead plaster.Obtained lead plaster is directly coated on negative electrode grid, sour place is rolled and drenched
It is put into controlled humidity high-low temperature chamber progress curing and drying program after reason, solidifies 36h under the conditions of 45 DEG C of relative humidity 95%, 85 DEG C
Dry 9h, obtains lead carbon battery negative plate.Using lead carbon battery negative plate, the lead-acid battery of the three above-mentioned preparations of positive four negative structure
It is 5.2Ah energy storage lean solution lead carbon battery that positive plate and glass fibre separator (AGM), which are assembled into rated capacity,.It is reflected and is weighed using Beijing
Rich solution internal hybrid lead carbon battery of the method as defined in " energy storage authenticates code fo practice with lead-acid accumulator " of authentication center to preparation
Carry out cycle life test.The result shows that rich solution lead carbon battery cycle life prepared by the present embodiment reaches 154 times, it is pair
Than 4.2 times of the lead-acid battery service life prepared by embodiment 3.
Comparative example 1
It weighs lead powder 100g, additive (barium sulfate 1.2g, lignin 0.2g), unmodified carbon fiber 1.0g and pours into paste mixing machine appearance
Dry-mixed 5 minutes in device, each component is mixed well, mixture is obtained.10g deionized water, stirring 5 are added in mixed powder
Minute, it is then slowly added into density 1.2g/cm310g sulfuric acid be uniformly mixing to obtain cathode lead plaster.Obtained lead carbon battery is born
Pole lead plaster is directly coated on negative electrode grid, is rolled and is put into controlled humidity high-low temperature chamber and is solidified after drenching acid processing
Drying program solidifies 36h under the conditions of 45 DEG C of relative humidity 95%, and 85 DEG C of dry 9h obtain lead carbon battery negative plate.Using preparation
Lead carbon battery negative plate as working electrode, traditional lead-acid battery positive plate makees that electrode is saturated mercuric sulfate electrode work and is joined
Than electrode, three-electrode system is collectively constituted, Electrochemical Characterization is carried out to lead carbon battery negative plate.Linear scan polarization curve
Potential window be open circuit potential to -1.5V；Cyclic voltammetric potential window is 0 to -1.5V.Linear polarization and cyclic voltammetry
As a result as depicted in figs. 1 and 2 respectively.
Comparative example 2
It weighs lead powder 500g, additive (barium sulfate 6g, lignin 1g), acetylene black 2.5g, polyester fiber 0.3g and pours into mixing paste
Dry-mixed 5 minutes in machine container, each component is mixed well, mixture is obtained.50g deionized water is added in mixed powder, stirs
It mixes 5 minutes, is then slowly added into density 1.2g/cm350g sulfuric acid be uniformly mixing to obtain cathode lead plaster.The lead carbon electricity that will be obtained
Pond cathode lead plaster is directly coated on negative electrode grid, is rolled and is put into controlled humidity high-low temperature chamber and carries out after drenching acid processing
Curing and drying program solidifies 36h under the conditions of 45 DEG C of relative humidity 95%, and 85 DEG C of dry 9h obtain lead-acid battery cathode plate.Using
The lead-acid battery cathode plate of preparation as working electrode, make to be saturated mercuric sulfate electrode to electrode and make reference by lead-acid battery positive plate
Electrode constitutes three-electrode system, carries out Electrochemical Characterization to lead-acid battery cathode plate.The current potential of linear scan polarization curve
Window is open circuit potential to -1.5V；Cyclic voltammetric potential window is 0 to -1.5V.Linear polarization and cyclic voltammetry result point
Not not as depicted in figs. 1 and 2.Using the lead-acid battery cathode plate of the three above-mentioned preparations of positive two negative structure, lead-acid battery positive plate and
It is 4.4Ah rich solution acid carbon battery that PE diaphragm, which is assembled into rated capacity,.Using SBAS0101-2014 " start-stop vehicle lead acid storage battery
Pond " method as defined in standard carries out cycle life test to the lead-acid battery of preparation.The result shows that lead prepared by the present embodiment
Sour battery cycle life is 18000 times.
Comparative example 3
Lead powder 100g, barium sulfate 1.2g, lignin 0.2g are weighed, pours into paste mixing machine container dry-mixed 5 minutes, fills each component
Divide and mix, obtains mixture.10g deionized water is added in mixed powder, stirs 5 minutes, is then slowly added into density 1.2
g/cm310g sulfuric acid be uniformly mixing to obtain cathode lead plaster.Obtained cathode lead plaster is directly coated on negative electrode grid, is carried out
It is put into controlled humidity high-low temperature chamber after rolling and leaching acid processing and carries out curing and drying program, under the conditions of 45 DEG C of relative humidity 95%
Solidify 36h, 85 DEG C of dry 9h obtain lead-acid battery cathode plate.It is negative using the lead-acid battery of the three above-mentioned preparations of positive four negative structure
It is 5.2Ah energy storage lean solution plumbic acid electricity that pole plate, lead-acid battery positive plate and glass fibre separator (AGM), which are assembled into rated capacity,
Pond.Rich solution of the method as defined in " energy storage lead-acid accumulator authenticates code fo practice " using Beijing Jian Heng authentication center to preparation
Lead-acid battery carries out cycle life test.The result shows that rich solution acid battery cycle life prepared by the present embodiment is 37 times.
Claims (4)
1. a kind of lead carbon battery cathode, cathode include lead material, it is characterised in that: contain the modification of 0.1~50wt% in cathode
Carbon fiber, the modified carbon fiber is by first activating carbon fiber, then is poisoned and obtained；Preferred modified carbon fiber
Dimension hplc is 0.5~5wt%, 1~3wt% of preferred modified carbon fiber content；
Activation is that carbon fiber is placed in CO230min~for 24 hours is roasted in gas stove at 600~900 DEG C；Poison is that will activate carbon fiber
Dimension is uniformly mixed with liberation of hydrogen inhibitor, in an inert atmosphere the processing 10min~for 24 hours at 100~500 DEG C；
Wherein, liberation of hydrogen inhibitor is containing metallic lead, tin, cerium, indium, bismuth, one of the aqueous solution of soluble-salt of samarium or two
Kind or more, soluble-salt is one of nitrate, acetate, acetate or two kinds or more, and concentration is 0.1wt%~correspondence gold
Belong to the saturated concentration of soluble-salt；
Inert atmosphere is one of nitrogen, argon gas, ammonia or two kinds or more.
2. a kind of preparation method of lead carbon battery cathode as described in claim 1, it is characterised in that: the cathode by walking as follows
Rapid preparation,
(1) take 100 mass parts of lead powder, barium sulfate and lignin mixture as additive 0.1-10 mass parts, modified carbon fiber 0.1
~50 mass parts stir dry-mixed 3~5min, mix well each component, obtain mixed powder；Barium sulfate and lignin in additive
Mixing mass ratio is 1:100~100:1.
(2) 10~21 mass parts deionized waters are added in mixed powder, stirs 3~6 minutes, is then slowly added into density 1.1
~1.4g/cm34~100 mass parts sulfuric acid be uniformly mixing to obtain cathode lead plaster；
(3) lead plaster is scratched onto grid, it is cured to be dried to obtain lead carbon battery negative electrode tab；In negative electrode tab active material with a thickness of
0.1~10mm；Solidification temperature is 10~100 DEG C, and relative humidity is 10~100%, curing time 1-50h；Drying temperature is
10~200 DEG C, relative humidity is 0~80%, and drying time is 1~50h.
3. a kind of application of cathode as described in claim 1, it is characterised in that: be applied in lead carbon battery as cathode.
4. application according to claim 3, it is characterised in that: be applied to internal hybrid lead carbon battery as cathode, more preferably
For start-stop or energy storage internal hybrid lead carbon battery.
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| CN110364737B (en) * | 2019-07-22 | 2022-08-09 | 雅迪科技集团有限公司 | Graphene composite conductive slurry and preparation method and application thereof |
| TWI701861B (en) * | 2019-08-23 | 2020-08-11 | 百樂電池股份有限公司 | Carbon lead battery |
| CN113036093A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Modified carbon material and preparation method and application thereof |
| CN113036127A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Composite carbon material and preparation method and application thereof |
| CN113036127B (en) * | 2019-12-09 | 2023-12-01 | 中国科学院大连化学物理研究所 | Composite carbon material and preparation method and application thereof |
| CN112968149A (en) * | 2019-12-13 | 2021-06-15 | 中国科学院大连化学物理研究所 | Application of electrode with residual ions |
| CN112968149B (en) * | 2019-12-13 | 2022-03-29 | 中国科学院大连化学物理研究所 | Application of electrode with residual ions |
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