CN116200149B - Preparation process of functionalized graphene adhesive for negative electrode of lead-carbon battery - Google Patents
Preparation process of functionalized graphene adhesive for negative electrode of lead-carbon battery Download PDFInfo
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- CN116200149B CN116200149B CN202211612247.XA CN202211612247A CN116200149B CN 116200149 B CN116200149 B CN 116200149B CN 202211612247 A CN202211612247 A CN 202211612247A CN 116200149 B CN116200149 B CN 116200149B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
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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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation process of a functionalized graphene adhesive for a lead-carbon battery cathode, which comprises the steps of dispersing GO in an ethanol aqueous solution, adding EDTA complex solution, and roasting to obtain RGO with porous carbon loaded on the surface; dispersing with 4-aminodiphenylamine by ultrasonic method, heating, stirring, reacting, sequentially adding hydrochloric acid, oxidant and sodium sulfate, performing electrochemical oxidation polymerization on the porous carbon pores to form doped polyaniline, washing and drying to obtain modified RGO; and adding the AMMA-MMA copolymer and the modified RGO into an organic solvent, and stirring to obtain the functionalized graphene adhesive. The high-activity porous carbon generated by pyrolysis is combined with the conductive polyaniline formed in the pores, so that more lead sulfate nucleation sites can be provided for forming lead sulfate tiny grains with high solubility, the lead-carbon battery has higher charge receiving capacity and circulation capacity, the negative grid, active substance lead powder and graphene can be glued into a whole, and the problems of reduced pole plate strength and active substance falling in the circulation process are effectively solved.
Description
Technical Field
The invention relates to the technical field of battery polar plate inactive materials, in particular to a preparation process of a functionalized graphene adhesive for a negative electrode of a lead-carbon battery.
Background
In various battery systems, lead-acid batteries with lead oxide as an anode, lead as a cathode and sulfuric acid as electrolyte have the advantages of safety, reliability, high recovery rate and high cost performance, are widely applied to the fields of electric bicycles, automobile start and stop, clean energy, industrial electronics, communication, military industry and the like, are the storage batteries with the largest yield at present, and account for more than 70% of the global market share.
The lead-carbon battery is formed by introducing a carbon material with the characteristic of an electric double layer capacitor into a negative electrode and then matching and assembling the negative electrode with a positive electrode, and is equivalent to combining the lead-acid battery and a super capacitor into a whole. At present, active carbon particles are introduced into a lead negative electrode, and the problems of sulfation of the negative electrode and low utilization rate of active substances can be improved by utilizing the higher specific surface area, specific capacitance and certain conductivity of the active carbon particles, but the hydrogen evolution overpotential of the active carbon particles is low, so that the hydrogen evolution of the negative electrode is serious, the water loss and the failure of the battery are easily caused, and the service life of the battery is influenced.
With further research, we find that the new technical bottleneck limits the further improvement of the cycle life, the high-current discharge capability and other performances of the battery, and the problems mainly come from two aspects: first, although functionalized graphene establishes a three-dimensional conductive network structure in the negative electrode of a lead-carbon battery, the reversible transformation of lead and lead sulfate will result in repeated changes in volume during cyclic charge and discharge. When the cycle times reach a certain degree, the three-dimensional conductive network inside the electrode starts to relax, so that the conductivity and strength of the electrode are reduced, and even the precipitation of the flaky graphene (carbon precipitation phenomenon) can be observed from the surface of the electrode; second, previous studies have shown that increasing the graphene content in the negative electrode can significantly solve the sulfation problem of the negative electrode and effectively extend the cycle life of the battery. However, the negative electrode active material lead is easily peeled off from the whole grid during high-rate circulation, because the difference in tap density between graphene and lead is extremely large, resulting in a significant decrease in the strength of the high-content graphene-lead negative electrode.
Disclosure of Invention
Aiming at the problems of reduced pole plate strength and falling of active substances in the cycle process of the lead-carbon battery negative electrode, the invention provides a preparation process of a functionalized graphene adhesive with high conductivity and high stability for the lead-carbon battery negative electrode.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the preparation process of the functionalized graphene adhesive for the negative electrode of the lead-carbon battery comprises the following steps:
s1, dispersing GO in an ethanol water solution, adding EDTA complex solution, uniformly stirring, heating to remove a solvent, and roasting at 850-950 ℃ in an N2 protective atmosphere to obtain RGO with porous carbon loaded on the surface;
s2, dispersing RGO and 4-aminodiphenylamine of which the surfaces are loaded with porous carbon in the step S2 in an ultrasonic manner to obtain graphene dispersion liquid, heating to 110-130 ℃ and stirring for reaction to obtain graphene mixed liquid of the surface-loaded porous carbon-loaded amino graphene and unreacted 4-aminodiphenylamine;
s3, sequentially adding hydrochloric acid, an oxidant and sodium sulfate into the graphene mixed solution in the step S2, controlling the temperature at 70-80 ℃, reacting for 90-120 min, performing electrochemical oxidative polymerization on the porous carbon pores to form doped polyaniline, and then washing and drying to obtain the surface double modified RGO;
s4, synthesizing an AMMA-MMA copolymer by taking methyl methacrylate and 9-anthracene-methyl methacrylate as raw materials, adding the AMMA-MMA copolymer and the surface double modified RGO of the step S3 into a low-boiling-point organic solvent, uniformly stirring, and heating to volatilize the low-boiling-point organic solvent to obtain the functionalized graphene adhesive.
Preferably, the preparation method of the EDTA complex solution comprises the following steps: EDTA is added into deionized water, and fully stirred and dissolved; then dropwise adding the metal soluble salt aqueous solution while stirring, and fully stirring to completely react.
Preferably, the metal-soluble brine solution is lead nitrate.
Preferably, the AMMA-MMA copolymer is prepared by the following steps: weighing methyl methacrylate, 9-anthracene-methyl methacrylate and azodiisobutyronitrile according to the proportion, dissolving with tetrahydrofuran, then introducing pure nitrogen for 20-30 min, and heating and refluxing for 20-24 h; then precipitating with methanol, and purifying with chloroform/methanol for 3 times; vacuum drying to obtain AMMA-MMA copolymer.
Preferably, the low boiling point organic solvent is tetrahydrofuran.
Preferably, the oxidant is ammonium persulfate.
Compared with the prior art, the invention has the following beneficial effects:
the graphene oxide GO edge is rich in oxygen-containing groups, so that the high conductivity of graphene is maintained, the hydrophilicity and aqueous solution dispersibility of the graphene surface are improved, EDTA complex liquid is uniformly distributed on the GO surface and forms an isolation effect for isolating graphene stacks on the graphene surface after pyrolysis, meanwhile, high-activity porous carbon generated by pyrolysis is combined with conductive polyaniline formed in porous carbon pores, the diffusion of sulfuric acid is facilitated, more lead sulfate nucleation sites can be provided for forming lead sulfate micro-grains with high solubility, the growth of lead sulfate is inhibited, the precipitation of lead sulfate on lead powder is reduced, meanwhile, the hydrogen evolution of active carbon is inhibited, and the lead carbon battery has higher charge receiving capacity and cycle capacity.
The AMMA-MMA copolymer has a large number of conjugated structures which are the same as those of graphene, on one hand, the graphene is adsorbed through pi-pi bond interaction, and on the other hand, the conductive performance is achieved by providing forward movement conditions for delocalization of free electrons, so that a conductive three-dimensional network with graphene and an AMMA conductive network are formed, and the internal resistance and the cycle performance of an active material can be remarkably reduced; meanwhile, the polyacrylate group is utilized to play a role in adhesion, so that the adhesive has excellent adhesive property on the active material and the negative grid, can bond the negative grid, the active material lead powder and the graphene into a whole, can keep the overall stability of the negative grid, the active material lead and the graphene after solidification, effectively solves the problems of plate strength reduction and active material shedding in a circulation process, and has high conductivity and high stability.
According to the preparation process scheme of the 4-aminodiphenylamine, on one hand, the pi-pi bond effect is utilized to improve the dispersion stability of graphene RGO after ultrasonic dispersion, so that graphene RGO aggregation is avoided, on the other hand, the surface of graphene RGO is modified after being heated to obtain aminated graphene, so that the aminated graphene is conveniently linked and modified with an AMMA-MMA copolymer in a covalent bond manner, and doped polyaniline is formed in porous carbon pores in an electrochemical oxidation polymerization method.
Detailed Description
Example 1
The embodiment provides a preparation process of a functionalized graphene adhesive for a negative electrode of a lead-carbon battery, which comprises the following steps:
1) Adding disodium ethylenediamine tetraacetate EDTA into deionized water, fully stirring and dissolving, dropwise adding a lead nitrate aqueous solution while stirring, and fully stirring and fully reacting to obtain EDTA complex solution;
2) Dispersing graphene oxide GO in an ethanol water solution, adding EDTA complex solution, uniformly stirring, heating to remove a solvent, and roasting at 950 ℃ in an N2 protective atmosphere to obtain reduced graphene oxide RGO with porous carbon loaded on the surface;
3) Dispersing the prepared RGO with porous carbon loaded on the surface and 4-aminodiphenylamine in an ultrasonic manner to obtain graphene dispersion liquid, heating to 125 ℃ and stirring for reaction to obtain graphene mixed liquid with porous carbon loaded on the surface and unreacted 4-aminodiphenylamine;
4) Sequentially adding hydrochloric acid, ammonium persulfate and sodium sulfate into the graphene mixed solution, controlling the temperature at 80 ℃, reacting for 90min, performing electrochemical oxidation polymerization on the porous carbon pores to form doped polyaniline, and then washing and drying to obtain surface double modified RGO;
5) Weighing methyl methacrylate MMA, methacrylic acid-9-anthracene-methyl ester AMMA and azodiisobutyronitrile according to the proportion, dissolving with tetrahydrofuran, then introducing pure nitrogen for 30min, and heating and refluxing for 24h; then precipitating with methanol, and purifying with chloroform/methanol for 3 times; vacuum drying to obtain AMMA-MMA copolymer;
6) And adding AMMA-MMA copolymer and surface double modified RGO into tetrahydrofuran, uniformly stirring, and heating to volatilize the tetrahydrofuran to obtain the functionalized graphene adhesive.
7) The prepared functionalized graphene adhesive is mechanically mixed with 20 parts of lead powder 80 parts, humic acid 0.6 parts, barium sulfate 0.4 parts, sodium lignosulfonate 0.2 parts and polypropylene fiber 0.05 parts, and sulfuric acid solution with the mass fraction of 40% is added into the mixture, and the mixture is stirred to prepare a lead plaster paste, so that the apparent density of the lead plaster is adjusted to be 4.2g/cm 3 And uniformly coating the lead plaster paste on a negative grid, and baking at 35 ℃ for 10 hours to obtain the negative plate.
Example 2
The embodiment provides a preparation process of a functionalized graphene adhesive for a negative electrode of a lead-carbon battery, which comprises the following steps:
1) Adding disodium ethylenediamine tetraacetate EDTA into deionized water, fully stirring and dissolving, dropwise adding a lead nitrate aqueous solution while stirring, and fully stirring and fully reacting to obtain EDTA complex solution;
2) Dispersing graphene oxide GO in an ethanol water solution, adding EDTA complex solution, uniformly stirring, heating to remove a solvent, and roasting at 900 ℃ in an N2 protective atmosphere to obtain reduced graphene oxide RGO with porous carbon loaded on the surface;
3) Dispersing the prepared RGO with porous carbon loaded on the surface and 4-aminodiphenylamine in an ultrasonic manner to obtain graphene dispersion liquid, heating to 120 ℃ and stirring for reaction to obtain graphene mixed liquid with porous carbon loaded on the surface and unreacted 4-aminodiphenylamine;
4) Sequentially adding hydrochloric acid, ammonium persulfate and sodium sulfate into the graphene mixed solution, controlling the temperature at 70 ℃, reacting for 120min, performing electrochemical oxidation polymerization on the porous carbon pores to form doped polyaniline, and then washing and drying to obtain surface double modified RGO;
5) Weighing methyl methacrylate MMA, methacrylic acid-9-anthracene-methyl ester AMMA and azodiisobutyronitrile according to the proportion, dissolving with tetrahydrofuran, then introducing pure nitrogen for 30min, and heating and refluxing for 24h; then precipitating with methanol, and purifying with chloroform/methanol for 3 times; vacuum drying to obtain AMMA-MMA copolymer;
6) And adding AMMA-MMA copolymer and surface double modified RGO into tetrahydrofuran, uniformly stirring, and heating to volatilize the tetrahydrofuran to obtain the functionalized graphene adhesive.
7) 25 parts of the prepared functionalized graphene adhesive, 75 parts of lead powder, 0.6 part of humic acid, 0.4 part of barium sulfate, 0.2 part of sodium lignosulfonate and 0.05 part of polypropylene fiber are mechanically mixed, added with a sulfuric acid solution with the mass fraction of 40%, stirred to prepare a lead plaster paste, and the apparent density of the lead plaster is adjusted to be 4.2g/cm 3 And uniformly coating the lead plaster paste on a negative grid, and baking at 35 ℃ for 10 hours to obtain the negative plate.
The negative plate obtained in the embodiment 1-2 is assembled into a 6-QTF-60 start-stop lead carbon super battery together with other necessary commercial components such as a positive electrode plate, a glass fiber cotton separator, a storage battery tank cover, electrolyte and the like, and the charge and discharge cycle times are tested by using GB/T18332.1, wherein the cycle times of the embodiment 1-2 under the conditions of 100% DOD/25 ℃/80% of residual capacity reach more than 700 times, the cycle times under the conditions of 60% DOD/25 ℃/80% of residual capacity reach more than 2500 times, and the capacity retention rate after 200 times of cycle reaches more than 96.5%.
While the basic principles and main features of the invention and advantages of the invention have been shown and described, it will be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are described in the foregoing description merely illustrate the principles of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined in the appended claims and their equivalents.
Claims (5)
1. The preparation process of the functionalized graphene adhesive for the negative electrode of the lead-carbon battery is characterized by comprising the following steps of: the method comprises the following steps:
s1, dispersing GO in an ethanol water solution, adding EDTA complex solution, uniformly stirring, heating to remove a solvent, and roasting at 850-950 ℃ in an N2 protective atmosphere to obtain RGO with porous carbon loaded on the surface;
s2, dispersing RGO and 4-aminodiphenylamine of which the surfaces are loaded with porous carbon in the step S2 in an ultrasonic manner to obtain graphene dispersion liquid, heating to 110-130 ℃ and stirring for reaction to obtain graphene mixed liquid of the surface-loaded porous carbon-containing aminated graphene and unreacted 4-aminodiphenylamine;
s3, sequentially adding hydrochloric acid, an oxidant and sodium sulfate into the graphene mixed solution in the step S2, controlling the temperature at 70-80 ℃, reacting for 90-120 min, performing electrochemical oxidative polymerization on the porous carbon pores to form doped polyaniline, and then washing and drying to obtain the surface double modified RGO;
s4, synthesizing an AMMA-MMA copolymer by taking methyl methacrylate and 9-anthracene-methyl methacrylate as raw materials, adding the AMMA-MMA copolymer and the surface double modified RGO of the step S3 into a low-boiling-point organic solvent, uniformly stirring, and heating and volatilizing the low-boiling-point organic solvent to obtain the functionalized graphene adhesive;
the preparation method of the AMMA-MMA copolymer comprises the following steps: weighing methyl methacrylate, 9-anthracene-methyl methacrylate and azodiisobutyronitrile according to the proportion, dissolving with tetrahydrofuran, then introducing pure nitrogen for 20-30 min, and heating and refluxing for 20-24 h; then precipitating with methanol, and purifying with chloroform/methanol for 3 times; vacuum drying to obtain AMMA-MMA copolymer.
2. The preparation process of the functionalized graphene adhesive for the negative electrode of the lead-carbon battery according to claim 1, which is characterized in that: the preparation method of the EDTA complex solution comprises the following steps: EDTA is added into deionized water, and fully stirred and dissolved; then dropwise adding the metal soluble salt aqueous solution while stirring, and fully stirring to completely react.
3. The process for preparing the functionalized graphene adhesive for the negative electrode of the lead-carbon battery according to claim 2, which is characterized in that: the metal soluble salt aqueous solution is lead nitrate.
4. The preparation process of the functionalized graphene adhesive for the negative electrode of the lead-carbon battery according to claim 1, which is characterized in that: the low-boiling point organic solvent is tetrahydrofuran.
5. The preparation process of the functionalized graphene adhesive for the negative electrode of the lead-carbon battery according to claim 1, which is characterized in that: the oxidant is ammonium persulfate.
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| CN202311298532.3A CN117431023A (en) | 2022-12-15 | 2022-12-15 | Lead plaster and preparation process of RGO with double surface modification |
| CN202211612247.XA CN116200149B (en) | 2022-12-15 | 2022-12-15 | Preparation process of functionalized graphene adhesive for negative electrode of lead-carbon battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108123136A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Lead carbon battery composite negative pole additive and lead carbon battery cathode and preparation and application |
| CN109390561A (en) * | 2018-09-27 | 2019-02-26 | 泉州市凯鹰电源电器有限公司 | A kind of lead negative and preparation method thereof of graphene lead carbon battery |
| WO2022131065A1 (en) * | 2020-12-14 | 2022-06-23 | 学校法人 関西大学 | Electrode for electrochemical devices and nonaqueous electrolyte secondary battery |
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| KR101902926B1 (en) * | 2012-01-18 | 2018-10-02 | 삼성전자주식회사 | Porous carbonaceous composite material, cathode and lithium air battery comprising the composite material, and method of preparing the composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108123136A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Lead carbon battery composite negative pole additive and lead carbon battery cathode and preparation and application |
| CN109390561A (en) * | 2018-09-27 | 2019-02-26 | 泉州市凯鹰电源电器有限公司 | A kind of lead negative and preparation method thereof of graphene lead carbon battery |
| WO2022131065A1 (en) * | 2020-12-14 | 2022-06-23 | 学校法人 関西大学 | Electrode for electrochemical devices and nonaqueous electrolyte secondary battery |
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