CN104201397A - Preparation method of lithium air battery electrode - Google Patents
Preparation method of lithium air battery electrode Download PDFInfo
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- CN104201397A CN104201397A CN201410411743.8A CN201410411743A CN104201397A CN 104201397 A CN104201397 A CN 104201397A CN 201410411743 A CN201410411743 A CN 201410411743A CN 104201397 A CN104201397 A CN 104201397A
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a preparation method of a lithium air battery electrode. The preparation method of the lithium air battery electrode comprises the following steps: sequentially growing or depositing a nitrogen-containing conductive polymer and a catalyst precursor on the surface of a piece of paper to obtain a piece of catalyst precursor/nitrogen-containing conductive polymer compound paper; putting the catalyst precursor/nitrogen-containing conductive polymer compound paper into an alkali solution containing nitrogen-containing organic matters for dipping, then putting the paper in a protection atmosphere for carbonizing and nitriding so as to obtain a metal nitride/nitrogen-containing layered porous carbon compound electrode by using a one-step method, wherein the metal nitride/nitrogen-containing layered porous carbon compound electrode is excellent in mechanical performance and electrochemical performance and high in energy density and uses a three-dimensional carbon fiber network structure as a self-supporting body. The compound electrode is capable of effectively reducing the charging and discharging polarization of the air battery and reducing the internal resistance of the battery. Compared with a conventional electrode preparation process, an adhesive and a coating process do not need to be used; the preparation method is easy to operate, environmentally-friendly, low in cost and capable of achieving the industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of lithium-air battery electrode, belong to lithium battery field.
Background technology
Along with the fast development of global economy, the mankind are more and more higher to the demand of energy, the pollution problem that the non-renewable and combustion of fossil fuel of traditional fossil fuel energy brings becomes increasingly conspicuous, and the exploitation of new energy technology becomes the mankind's focus and study hotspot gradually.In recent decades, along with lithium ion battery is in the successful Application of commercial field, people have strengthened the research taking lithium as basic high-performance chemical power supply.
Lithium-air battery is due to very high energy density, becomes a new generation's accumulation power supply in future of tool potentiality.Lithium-air battery is taking lithium metal as negative pole, and porous electrode is anodal, and oxygen is as a kind of battery system of positive active material.In discharge process, oxygen enters battery by the external world, under catalyst action with from negative pole, flows through the electronics coming and the Li transmitting through electrolyte through external circuit
+generating electrodes reaction, generates with lithium peroxide (Li
2o
2) be main product, and release energy.In theory, oxygen is unrestricted as anode reactant, and the capacity of battery only depends on lithium electrode, and its theoretical specific energy is up to 11680Wh/kg, close to the energy density (13000Wh/kg left and right) of traditional fossil fuel.Therefore, lithium-air battery is considered to the first-selected power source of power vehicle of future generation, becomes the power conversion system receiving much concern at present.But due to the decomposition of electrolyte in cyclic process, discharge and recharge coulomb efficiency low, the critical defect such as cycle performance is poor has limited the development of lithium-air battery, to such an extent as to it is not yet universal so far.In lithium-air battery charge and discharge process, serious polarization phenomena and the obstruction in porous anode duct are the basic reasons that causes these defects.Therefore, develop and design novel lithium-air battery porous anode, the development of lithium-air battery is had to profound significance.
The anodal normal metallic catalyst that uses of lithium-air battery, is used for improving lithium-air battery efficiency for charge-discharge, improves battery cycle life, and metallic catalyst mainly comprises: noble metal catalyst, catalyst of transition metal oxide and metal nitride eelctro-catalyst etc.In these catalyst, transition metal nitride catalyst material not only self has good catalytic performance, and has good electric conductivity.
At present, the preparation method of lithium-air battery positive pole, is the mixed slurry that obtains catalyst-carbon composite, bonding agent and conductive agent by mechanical mixture, then slurry is coated on porous current collector.Therefore,, in the preparation process of lithium-air battery positive pole, inevitably to use bonding agent, conductive agent and collector.These materials add the energy density that greatly reduces battery, moreover, the use of bonding agent also can cause the increase of anodal impedance.
Summary of the invention
The object of the invention is to be to provide a kind of mechanical performance and electro-chemical properties good, energy density is high, can effectively reduce lithium-air battery and discharge and recharge polarization, reduce the preparation method of the lithium-air battery electrode of the internal resistance of cell, the preparation technology of the relatively existing electrode of this preparation method, without using binding agent and coating process, simple to operate, environmental protection, cost are low, can suitability for industrialized production.
The invention provides a kind of preparation method of lithium-air battery electrode, this preparation method grows successively on scraps of paper surface or deposits nitrogenous conducting polymer and catalyst precursor, obtains catalyst precursor/nitrogenous conductive polymer composite scraps of paper; Gained catalyst precursor/nitrogenous conductive polymer composite scraps of paper are put into after the aqueous slkali dipping that contains itrogenous organic substance; be placed in protective atmosphere; carry out charing and nitrogenize at 700～1000 DEG C, obtain the metal nitride/nitrogenous level hole carbon composite electrode taking three-dimensional carbon fibrillar meshwork structure as self-supporter.
The preparation method of lithium-air battery electrode of the present invention also comprises following preferred version.
In preferred preparation method, scraps of paper thickness is 10～50 microns; The three-dimensional carbon fibrillar meshwork structure self-supporter that preferred scraps of paper thickness generates charing has better mechanical performance.
The scraps of paper in preferred preparation method are one or several in filter paper, printing paper, writing paper, wrapping paper, living-hygienic paper using, most preferably are filter paper.
Alkali in the aqueous slkali that contains itrogenous organic substance in preferred preparation method is one or more the alkali-metal hydroxide in potassium hydroxide, NaOH, lithium hydroxide; Preferred alkali metal hydroxide has strong basicity, can play better activation.
In preferred preparation method, itrogenous organic substance is one or more in urea, melamine, diethylamine, aniline, dicyandiamide, formamide; Preferred itrogenous organic substance is micromolecular compound, is more conducive to doping in three-dimensional carbon fibrillar meshwork structure that nitrogen element generates in charing and the generation of metal nitride.
In the aqueous slkali that contains itrogenous organic substance in preferred preparation method, the mass ratio of alkali-metal hydroxide and itrogenous organic substance is 1:1～5:1.In preferred preparation method, alkali-metal hydroxide and itrogenous organic substance are composite in suitable ratio, alkali-metal hydroxide plays reaming effect on the one hand, react with itrogenous organic substance on the other hand, generate ammonia, not only provide nitride catalyst to generate required nitrogenous source, and nitrogen doping effect in nitrogenous layer time hole carbon in combination electrode can be effectively provided.
In preferred preparation method, the mass ratio of alkali-metal hydroxide and catalyst precursor/nitrogenous conductive polymer composite scraps of paper is 1:1～3:1.Preferred alkali-metal hydroxide and catalyst precursor/nitrogenous conductive polymer composite scraps of paper quality proportioning is more conducive to improve the activation reaming effect to composite paper in carbonization process of alkali-metal hydroxide.
In preferred preparation method, catalyst precursor is one or more in oxide or the hydroxide of iron, nickel, cobalt or manganese.One or more in the nitride that the corresponding catalyst of producing is iron, nickel, cobalt or manganese.
In preferred preparation method, nitrogenous conducting polymer is one or more in polypyrrole, polyaniline, poly-dopamine, polyacrylonitrile, polyacrylamide.
In preferred preparation method, charing and nitridation time are 2～10 hours; Preferred charing and nitridation time are more conducive to the generation of metal nitride catalyst agent and three-dimensional carbon fibrillar meshwork structure, and the performance of the activation reaming effect of alkali.
The nitrogen content of the metal nitride/nitrogenous level hole carbon composite electrode taking three-dimensional carbon fibrillar meshwork structure as self-supporter in preferred preparation method is 15～26wt%.The raising of nitrogen content in described combination electrode, not only effectively improves the conductivity of material, can also improve the catalysis efficiency of metal nitride.
In preferred preparation method, the scraps of paper are by charing generating three-dimensional carbon fiber network structure, and specific area is 500～1000m
2/ g.
In preferred preparation method, nitrogenous conducting polymer amount is the scraps of paper 0.2～10 times.
In preferred preparation method, protective atmosphere is nitrogen or argon gas.
Beneficial effect of the present invention:
(1) the metal nitride taking three-dimensional carbon fibrillar meshwork structure as the self-supporter/nitrogenous level hole carbon composite electrode that prepared by the present invention nitrogenous abundant, specific area is large, has greatly improved mechanical performance and the chemical property of lithium air electrode.
(2) metal nitride taking three-dimensional carbon fibrillar meshwork structure as self-supporter/nitrogenous level hole carbon composite electrode that prepared by the present invention, catalyst material metal nitride is distributed in the surface and pore structure of nitrogenous level hole carbon of collection liquid surface uniformly, and the pore structure of the middle-level hole of electrochemical reaction process carbon prosperity is not only stored discharging product Li
2o
2effective, be conducive to active material O simultaneously
2transmission, improved the chemical property of battery.
(3) in preparation method of the present invention, do not need to use binding agent and coating process, directly use as electrode, saved operation, ensured the effectively compound of catalyst and porous carbon materials, the energy density of electrode is obviously promoted simultaneously.
(4) preparation method of the present invention adopts alkali metal hydroxide and itrogenous organic substance mixed solution to flood before the charing of catalyst precursor/nitrogenous conductive polymer composite scraps of paper, in heat treatment process, alkali metal highly basic, in playing activation reaming effect, can react with itrogenous organic substance and discharge NH
3thereby can avoid using under the condition of the strong and expensive ammonia of corrosivity, one step realizes the generation of charing, nitrating and the nitride catalyst of material, nitrogen doping can not only effectively improve the conductivity of Carbon Materials, can also make the catalysis efficiency of nitrided iron catalyst obtain General Promotion.
(5) adopt base metal as eelctro-catalyst, material source is extensive, has reduced eelctro-catalyst cost, and simultaneously selected metal oxide catalyst, himself has excellent electrocatalysis characteristic.
(6) simple to operate, cost is low, is easy in industrial enforcement and production in enormous quantities.
Brief description of the drawings
[Fig. 1] is by the SEM figure after filter paper carbonization used in embodiment 1.
[Fig. 2] is the SEM figure that obtains carbon fiber/nitrogenous level hole nanocarbon/metal nitride catalyst composite construction by embodiment 1.
[Fig. 3] is 100 the discharge capacity curve charts of lithium-air battery that obtain by embodiment 1.
[Fig. 4] is the lithium-air battery first charge-discharge capacity curve figure obtaining by embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details, but is not restricted to the protection range of invention.
Embodiment 1
0.1 gram of polyaniline and 0.1 gram of iron hydroxide by liquid deposition or to be grown in thickness be that 20 microns, quality are the filter paper surface of 0.02 gram, are obtained to catalyst precursor/nitrogenous conductive polymer composite scraps of paper after dry.Gained catalyst precursor/nitrogenous conductive polymer composite scraps of paper were put into after potassium hydroxide solution (0.6 gram of potassium hydroxide) dipping a period of time of containing 0.2 gram of urea; be placed in protection nitrogen atmosphere; carry out charing and nitrogenize 5 hours at 800 DEG C, obtain the metal nitride/nitrogenous level hole carbon composite electrode of the nitrogenous 18wt% taking three-dimensional carbon fibrillar meshwork structure as self-supporter.The electrode and the cathode of lithium that adopt the present embodiment to prepare are assembled into button cell, under room temperature, under the current density of 200mA/g, carry out constant current charge-discharge test in the voltage range of 2.0～4.2V.First discharge specific capacity can reach 14000mAh/g, charge ratio capacity can reach about 13700mAh/g, 100 circles that can circulate in the restriction specific discharge capacity situation that is 1000mAh/g, illustrate that the lithium-air battery electrode that embodiment 1 prepares shows excellent chemical property.
The filter paper that can find out charing in Fig. 1 has the three-dimensional net structure that carbon fiber is formed by connecting;
In Fig. 2, can find out the lithium-air battery electrode making, show the evenly composite network structure of coated three-dimensional carbon fiber self-supporter of level hole carbon and metal nitride.
In Fig. 3, showing to adopt three-dimensional carbon fibrillar meshwork structure is metal nitride/nitrogenous level hole carbon composite electrode of self-supporter, under room temperature under the current density of 200mA/g constant current charge-discharge, 100 circles that can circulate in the restriction specific discharge capacity situation that is 1000mAh/g, show excellent cycle performance.
In Fig. 4, showing to adopt three-dimensional carbon fibrillar meshwork structure is metal nitride/nitrogenous level hole carbon composite electrode of self-supporter, under room temperature under the current density of 200mA/g constant current charge-discharge, specific discharge capacity can reach about 14000mAh/g, charge ratio capacity can reach about 13700mAh/g, shows excellent invertibity; Charging voltage platform is 3.8V simultaneously, and charging voltage platform is 2.8V, embodies less overpotential, illustrates that prepared combination electrode has excellent catalytic capability and chemical property.
Embodiment 2
By 0.1 gram of poly-dopamine and 0.05 gram of cobalt oxide by liquid deposition or be grown in thickness be 50 microns, quality is 0.075 gram of printing paper surface, obtains catalyst precursor/nitrogenous conductive polymer composite scraps of paper after dry.Gained catalyst precursor/nitrogenous conductive polymer composite scraps of paper were put into after sodium hydroxide solution (0.4 gram of NaOH) dipping a period of time of containing 0.3 gram of melamine; be placed in protection nitrogen atmosphere; carry out charing and nitrogenize 10 hours at 900 DEG C, obtain the metal nitride/nitrogenous level hole carbon composite electrode of the nitrogenous 25wt% taking three-dimensional carbon fibrillar meshwork structure as self-supporter.The electrode and the cathode of lithium that adopt the present embodiment to prepare are assembled into button cell, under room temperature, under the current density of 200mA/g, carry out constant current charge-discharge test in the voltage range of 2.0～4.2V.First discharge specific capacity can reach 13500mAh/g, charge ratio capacity can reach about 13200mAh/g, 100 circles that can circulate in the restriction specific discharge capacity situation that is 1000mAh/g, illustrate that the lithium-air battery electrode that embodiment 2 prepares shows excellent chemical property.
Embodiment 3
0.05 gram of polypyrrole and 0.2 gram of nickel oxide by liquid deposition or to be grown in thickness be that 10 microns, quality are the writing paper surface of 0.05 gram, are obtained to catalyst precursor/nitrogenous conductive polymer composite scraps of paper after dry.Gained catalyst precursor/nitrogenous conductive polymer composite scraps of paper were put into after lithium hydroxide solution (0.5 gram of lithium hydroxide) dipping a period of time of containing 0.2 gram of melamine; be placed in protection nitrogen atmosphere; carry out charing and nitrogenize 2 hours at 700 DEG C, obtain the metal nitride/nitrogenous level hole carbon composite electrode of the nitrogenous 15wt% taking three-dimensional carbon fibrillar meshwork structure as self-supporter.The electrode and the cathode of lithium that adopt the present embodiment to prepare are assembled into button cell, under room temperature, under the current density of 200mA/g, carry out constant current charge-discharge test in the voltage range of 2.0～4.2V.First discharge specific capacity can reach 13100mAh/g, charge ratio capacity can reach about 12800mAh/g, 100 circles that can circulate in the restriction specific discharge capacity situation that is 1000mAh/g, illustrate that the lithium-air battery electrode that embodiment 3 prepares shows excellent chemical property.
Embodiment 4
0.1 gram of polyaniline and 0.2 gram of cobalt hydroxide by liquid deposition or to be grown in thickness be the filter paper surface that 10 microns, quality are 0.01g, are obtained to catalyst precursor/nitrogenous conductive polymer composite scraps of paper after dry.Gained catalyst precursor/nitrogenous conductive polymer composite scraps of paper were put into after potassium hydroxide solution (0.32 gram of potassium hydroxide) dipping a period of time of containing 0.1 gram of melamine; be placed in protection nitrogen atmosphere; carry out charing and nitrogenize 2 hours at 800 DEG C, obtain the metal nitride/nitrogenous level hole carbon composite electrode of the nitrogenous 19wt% taking three-dimensional carbon fibrillar meshwork structure as self-supporter.The electrode and the cathode of lithium that adopt the present embodiment to prepare are assembled into button cell, under room temperature, under the current density of 200mA/g, carry out constant current charge-discharge test in the voltage range of 2.0～4.2V.First discharge specific capacity can reach 13800mAh/g, charge ratio capacity can reach about 13500mAh/g, 100 circles that can circulate in the restriction specific discharge capacity situation that is 1000mAh/g, illustrate that the lithium-air battery electrode that embodiment 4 prepares shows excellent chemical property.
Claims (10)
1. a preparation method for lithium-air battery electrode, is characterized in that, grows successively or deposit nitrogenous conducting polymer and catalyst precursor on scraps of paper surface, obtains catalyst precursor/nitrogenous conductive polymer composite scraps of paper; Gained catalyst precursor/nitrogenous conductive polymer composite scraps of paper are put into after the aqueous slkali dipping that contains itrogenous organic substance; be placed in protective atmosphere; at 700～1000 DEG C, carry out charing and nitrogenize, obtain the metal nitride/nitrogenous level hole carbon composite electrode taking three-dimensional carbon fibrillar meshwork structure as self-supporter.
2. preparation method according to claim 1, is characterized in that, described scraps of paper thickness is 10～50 microns.
3. preparation method according to claim 1 and 2, is characterized in that, the described scraps of paper are one or several in filter paper, printing paper, writing paper, wrapping paper, living-hygienic paper using.
4. preparation method according to claim 1, is characterized in that, the alkali in the aqueous slkali of described itrogenous organic substance is one or more the alkali-metal hydroxide in potassium hydroxide, NaOH, lithium hydroxide; Itrogenous organic substance in the aqueous slkali of described itrogenous organic substance is one or more in urea, melamine, diethylamine, aniline, dicyandiamide, formamide.
5. preparation method according to claim 4, is characterized in that, in the described aqueous slkali that contains itrogenous organic substance, the mass ratio of alkali-metal hydroxide and itrogenous organic substance is 1:1～5:1.
6. according to the preparation method described in claim 1 or 4, it is characterized in that, the mass ratio of described alkali-metal hydroxide and catalyst precursor/nitrogenous conductive polymer composite scraps of paper is 1:1～3:1.
7. preparation method according to claim 1, is characterized in that, described catalyst precursor is one or more in oxide or the hydroxide of iron, nickel, cobalt or manganese.
8. preparation method according to claim 1, is characterized in that, described nitrogenous conducting polymer is one or more in polypyrrole, polyaniline, poly-dopamine, polyacrylonitrile, polyacrylamide.
9. preparation method according to claim 1, is characterized in that, described charing and nitridation time are 2～10 hours.
10. preparation method according to claim 1, is characterized in that, the nitrogen content of the described metal nitride taking three-dimensional carbon fibrillar meshwork structure as self-supporter/nitrogenous level hole carbon composite electrode is 15～26wt%.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140541A (en) * | 2015-07-30 | 2015-12-09 | 苏州大学 | Air electrode for adhesive-free lithium-air battery and fabrication method and application of air electrode |
| CN107317040A (en) * | 2017-06-22 | 2017-11-03 | 清华大学 | The floatation type gas-diffusion electrode reacted for gas consumption and its preparation |
| CN107394140A (en) * | 2017-07-05 | 2017-11-24 | 河南师范大学 | The preparation method of the sodium iron-based prussian blue electrode material of poly-dopamine cladding |
| CN109378485A (en) * | 2018-11-03 | 2019-02-22 | 东华大学 | A kind of nonmetallic pyridine nitrogen-doped carbon composite material and preparation method and application based on nano wire |
| CN110189928A (en) * | 2019-06-21 | 2019-08-30 | 中南林业科技大学 | A kind of layer structure paper base carbon electrode preparation method |
| CN110247060A (en) * | 2019-06-30 | 2019-09-17 | 哈尔滨工业大学 | PANI/Go/PAN nanofiber membrane composite potassium cathode of air battery and preparation method thereof |
| CN110265678A (en) * | 2019-07-25 | 2019-09-20 | 河南师范大学 | A kind of preparation method and applications of the NiO@NC bifunctional electrocatalyst with core-shell structure |
| CN112599362A (en) * | 2020-12-11 | 2021-04-02 | 桐乡市融杭科技合伙企业(有限合伙) | Preparation method and application of nitrogen-sulfur doped mesoporous carbon electrode material with uniformly distributed pores |
| EP3945067A1 (en) | 2020-07-27 | 2022-02-02 | Universitat Rovira I Virgili | A method for producing an s-triazine or s-heptazine-based polymeric or oligomeric materials and s-triazine or s-heptazine-based coatings and composites derived therefrom |
| CN114335705A (en) * | 2020-09-28 | 2022-04-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Integrated all-solid-state battery and preparation method thereof |
| US11876207B2 (en) | 2016-07-01 | 2024-01-16 | Nippon Telegraph And Telephone Corporation | Battery and method of manufacturing cathode of the same |
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| CN105140541A (en) * | 2015-07-30 | 2015-12-09 | 苏州大学 | Air electrode for adhesive-free lithium-air battery and fabrication method and application of air electrode |
| US11876207B2 (en) | 2016-07-01 | 2024-01-16 | Nippon Telegraph And Telephone Corporation | Battery and method of manufacturing cathode of the same |
| CN107317040A (en) * | 2017-06-22 | 2017-11-03 | 清华大学 | The floatation type gas-diffusion electrode reacted for gas consumption and its preparation |
| CN107394140A (en) * | 2017-07-05 | 2017-11-24 | 河南师范大学 | The preparation method of the sodium iron-based prussian blue electrode material of poly-dopamine cladding |
| CN109378485B (en) * | 2018-11-03 | 2022-07-12 | 东华大学 | Nanowire-based nonmetal pyridine nitrogen-doped carbon composite material and preparation method and application thereof |
| CN109378485A (en) * | 2018-11-03 | 2019-02-22 | 东华大学 | A kind of nonmetallic pyridine nitrogen-doped carbon composite material and preparation method and application based on nano wire |
| CN110189928A (en) * | 2019-06-21 | 2019-08-30 | 中南林业科技大学 | A kind of layer structure paper base carbon electrode preparation method |
| CN110189928B (en) * | 2019-06-21 | 2021-01-26 | 中南林业科技大学 | Preparation method of paper-based carbon electrode with layered structure |
| CN110247060A (en) * | 2019-06-30 | 2019-09-17 | 哈尔滨工业大学 | PANI/Go/PAN nanofiber membrane composite potassium cathode of air battery and preparation method thereof |
| CN110265678A (en) * | 2019-07-25 | 2019-09-20 | 河南师范大学 | A kind of preparation method and applications of the NiO@NC bifunctional electrocatalyst with core-shell structure |
| WO2022023025A1 (en) | 2020-07-27 | 2022-02-03 | Universitat Rovira I Virgili | A METHOD FOR PRODUCING AN S-TRIAZINE or S-HEPTAZINE-BASED POLYMERIC OR OLIGOMERIC MATERIALS AND S-TRIAZINE or S-HEPTAZINE-BASED COATINGS AND COMPOSITES DERIVED THEREFROM |
| EP3945067A1 (en) | 2020-07-27 | 2022-02-02 | Universitat Rovira I Virgili | A method for producing an s-triazine or s-heptazine-based polymeric or oligomeric materials and s-triazine or s-heptazine-based coatings and composites derived therefrom |
| CN114335705A (en) * | 2020-09-28 | 2022-04-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Integrated all-solid-state battery and preparation method thereof |
| CN112599362A (en) * | 2020-12-11 | 2021-04-02 | 桐乡市融杭科技合伙企业(有限合伙) | Preparation method and application of nitrogen-sulfur doped mesoporous carbon electrode material with uniformly distributed pores |
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