CN107634192B - Negative electrode material for zinc-based battery and preparation method thereof - Google Patents
Negative electrode material for zinc-based battery and preparation method thereof Download PDFInfo
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Abstract
The invention provides a negative electrode material for a zinc-based battery, which is in a structure that zinc oxide particles are coated by graphene laminas, wherein the mass percentage of zinc oxide in the negative electrode material is 60-95%; the thickness of the graphene sheet layer is 0.5-10 nm, and the plane size of the graphene is 500 nm-50 mu m. The invention also provides a preparation method of the cathode material. The invention adopts zinc oxide with low price or precursor salt thereof and graphene oxide as raw materials; the negative electrode material for the zinc-based battery with the graphene-coated zinc oxide structure is prepared by a simple hydrothermal method, a solvothermal method or a coprecipitation method. The zinc-based battery assembled by using the graphene-coated zinc oxide composite material as the negative electrode has an output voltage of 1.2-1.8V; the obtained graphene-coated zinc oxide composite material has large specific capacity when used as a zinc-based battery negative electrode material, and has super-good cycle performance.
Description
Technical Field
The invention belongs to the field of carbon material preparation, and particularly relates to a preparation method of graphene.
Background
With the increasing environmental pollution and the gradual depletion of fossil energy, the demand for new renewable energy sources for sustainable development is continuously increasing. The rechargeable zinc-based battery is the first choice of energy storage equipment such as electric vehicles, emergency energy sources and energy storage power stations due to the excellent characteristics of the rechargeable zinc-based battery, and is an ideal potential power supply system of future space technology and high-end energy storage systems. The preparation of the novel negative electrode material for the rechargeable zinc-based battery, which has high charge storage density, rapid charge and discharge characteristics, good charge and discharge efficiency, long cycle life and low cost, is one of the most active branches of the research direction at present.
The zinc oxide as the common negative electrode material of the zinc-based battery has the advantages of easily obtained raw materials, low price and environmental protection, and is the most widely researched negative electrode material of the zinc-based battery. However, zinc oxide has the disadvantages of poor stability in an alkaline environment, easy dissolution and deformation, easy formation of dendrites in the charging and discharging processes, and poor conductivity, so that the zinc oxide serving as a zinc-based battery negative electrode material has the disadvantages of low specific capacity and poor cycle stability. Therefore, research in this field is focused on research, development and preparation technology of novel zinc-based battery negative electrode materials with high capacity, high power, long service life and low cost.
Graphene is a novel two-dimensional material, has the advantages of large specific surface area, good conductivity, stable structure and the like, and is widely concerned in the field of energy storage in recent years. The graphene-coated zinc oxide has the advantages of high conductivity, large specific surface area and good stability, can effectively inhibit the dissolution and deformation of the zinc oxide, can effectively disperse charge-discharge current, and reduces the surface current density, thereby inhibiting the formation of branch crystals and further improving the cycle stability. Therefore, the zinc-based battery negative electrode material has high specific capacity, high rate performance and long cycle life. However, the practical application of the graphene-coated zinc oxide is still limited by the limited preparation method at present.
Disclosure of Invention
The invention aims to overcome the defects of low yield, high pollution, complex process and the like of the existing graphene production method and provide the method for preparing the graphene by liquid phase stripping, which has the advantages of low production cost, environmental friendliness, high yield and suitability for industrial production.
The technical scheme for realizing the purpose of the invention is as follows:
the negative electrode material for the zinc-based battery is of a structure that zinc oxide particles are coated by graphene laminas, and the mass percentage of zinc oxide in the negative electrode material is 60-95%; the thickness of the graphene sheet layer is 0.5-10 nm, and the plane size of the graphene is 500 nm-50 mu m.
The coating structure provided by the invention is prepared by taking graphene oxide (graphene) and zinc oxide (or a zinc oxide precursor) as raw materials through a hydrothermal method, a solvothermal method or a coprecipitation method. When the composite material is used as a zinc-based battery negative electrode material, the reversible capacity is 300-650 mAh/g.
The preparation method of the negative electrode material for the zinc-based battery comprises the following steps:
(1) uniformly dispersing a zinc-containing compound and a graphite material in water and/or an organic solvent, and then reacting in a normal-pressure reactor or a hydrothermal kettle at the reaction temperature of 25-300 ℃, wherein the feeding mass ratio of the zinc-containing compound to the graphite material is 0.8-12: 1;
the zinc-containing compound is zinc oxide or a zinc oxide precursor, and the zinc oxide precursor is selected from one of zinc salt, zinc-based hydrotalcite and zinc-containing organic matter; the graphite material is graphene or graphene oxide; the organic solvent is one or a combination of ethanol, propanol, ethylene glycol, isopropanol and methyl pyrrolidone; the reaction is one or more of hydrothermal reaction, solvothermal reaction and coprecipitation reaction;
(2) drying the product system of the step (1) by any one drying method selected from vacuum drying, freeze drying and supercritical drying.
Wherein in the step (1), the zinc oxide is prepared by one of preparation methods of a calcining method, a solvothermal method, a hydrothermal method, a coprecipitation method and a vapor deposition method, and the size of the zinc oxide is 10 nm-50 μm; the zinc salt is one or more of zinc nitrate, zinc acetate, zinc chloride, zinc sulfate and zinc stannate; the zinc-based hydrotalcite is one or more of zinc-aluminum hydrotalcite, zinc-aluminum-magnesium hydrotalcite, zinc-aluminum-copper hydrotalcite, zinc-aluminum-cerium hydrotalcite and zinc-aluminum-lanthanum hydrotalcite.
Further, the graphite material is graphene oxide, and the graphite oxide is prepared by an improved hummers' method, which specifically comprises the following steps: mixing graphite flake and sodium nitrate, adding concentrated sulfuric acid, and slowly adding KMnO at a temperature lower than 4 deg.C4Stirring and reacting for 1h at the temperature lower than 4 ℃, then heating to 30-40 ℃ for reacting for 0.5-1 h, then slowly adding deionized water until the deionized water is deionizedHeating to boil after water is completely added, and keeping the reaction for 30 min; wherein the graphite flake, sodium nitrate, concentrated sulfuric acid and KMnO4The mass ratio of (1): 0.1-0.8: 20-50: 2 to 4.
When the zinc oxide or the zinc oxide precursor selected by the coprecipitation method in the step (1) cannot be coprecipitated with the graphene oxide, an additive is adopted; when the precursor used in step (1) can be co-precipitated with graphene oxide, the additive may or may not be added.
Further, an additive is added into the dispersion system of the zinc-containing compound and the graphite material, and the additive is a silane coupling agent and/or a surfactant; one or more selected from aminopropyltriethoxysilane, CTAB, Sodium Dodecyl Sulfate (SDS), PVP, F127 and the like, wherein the mass ratio of the additive to the zinc-containing compound is 1: 0.8 to 1.5.
As a preferred technical scheme of the invention, the step (1) is as follows: dispersing zinc oxide in water, adding an additive, and stirring for 10-30 hours; dispersing a graphite material in water, slowly adding a zinc oxide solution into an aqueous solution of the graphite material, and stirring at room temperature to perform coprecipitation for 2-4 hours. The addition may be dropwise or slowly poured.
When the solvent adopted in the step (1) has no reducibility, a reducing agent is required to be added; when the solvent used in step (1) has reducing properties, the reducing agent may or may not be added.
Further, after a dispersion system is formed in the step (1), a reducing agent is added into the dispersion system to perform a reduction reaction, wherein the reducing agent is selected from one or more of hydrazine hydrate, sodium borohydride, potassium borohydride and hydrogen, and the temperature of the reduction reaction is 50-90 ℃.
Optionally, after the step (2), performing heat treatment on the obtained product, wherein the treatment temperature is 200-1000 ℃, and the treatment time is 0.5-10 hours.
The battery containing the negative electrode material for the zinc-based battery is provided.
The manufacturing method of the negative electrode of the battery comprises the following steps: the negative electrode material, the binder and the conductive agent of claim 1 are mixed and coated on a current collector; the positive electrode of the battery is nickel hydroxide.
The binder and the conductive agent may be those known in the art, such as PTFE, acetylene black, super carbon black, etc., and the current collector may be one of a copper mesh, a copper foil, and an aluminum foil, but is not limited thereto.
Compared with the prior art, the invention has the following advantages:
(1) the invention adopts zinc oxide with low price or precursor salt thereof and graphene oxide as raw materials; (2) the negative electrode material for the zinc-based battery with the graphene-coated zinc oxide structure is prepared by a simple hydrothermal method, a solvothermal method or a coprecipitation method. (3) The zinc-based battery assembled by using the graphene-coated zinc oxide composite material as the negative electrode has an output voltage of 1.2-1.8V; (4) the obtained graphene-coated zinc oxide composite material has large specific capacity (the specific capacity can reach 300-700 mAh/g during 1C charging and discharging) when being used as a zinc-based battery negative electrode material; (5) when the obtained graphene-coated zinc oxide composite material is used as a zinc-nickel battery cathode material, the graphene-coated zinc oxide composite material has an ultra-good cycle performance (200-500 mAh/g can be maintained after 100 times of repeated charge and discharge under the 1C charge and discharge condition).
In conclusion, the composite material has high conductivity, super-excellent high-rate performance and good cycle stability, is a very ideal zinc-based battery negative electrode material, and can be widely applied to the fields of various portable electronic devices, electric automobiles, aerospace and the like; in addition, the composite material can be prepared from low-price raw materials through a process with high repeatability, a simple process and less time consumption, and is suitable for industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of the material of example 2.
Fig. 2 is a reversible charge-discharge curve of example 2.
FIG. 3 is a scanning electron micrograph of the material of example 6.
Figure 4 is an XRD pattern of the material of example 6.
Detailed Description
The following detailed description is illustrative of the invention and is not to be construed as limiting the invention.
In the embodiment, the preparation method of the graphene oxide is a modified hummers' method. Uniformly mixing 10g of graphite flake and 5g of sodium nitrate, adding 220mL of concentrated sulfuric acid, and slowly adding 30g of KMnO within 30min under the condition of stirring at the temperature lower than 4 DEG C4And then stirring and reacting for 1h at the temperature of less than 4 ℃, then heating to 35 ℃ for reacting for 30min, then slowly adding 450mL of deionized water, heating to boiling after water is completely added, keeping the reaction for 30min, and then cooling, washing, dialyzing, concentrating and freeze-drying to obtain the graphene oxide.
Through SEM observation, the thickness of the prepared graphene oxide sheet layer is 0.5-10 nm, and the plane size is 500 nm-50 μm.
The zinc oxide by calcining method adopted in the embodiment is commercially available, and the particle size distribution is in the range of 10 nanometers to 50 micrometers.
In the examples, unless otherwise specified, the technical means used are those conventional in the art.
Example 1:
a graphene-coated zinc oxide composite material is prepared by the following steps:
(1) mixing 80g of zinc oxide obtained by a calcination method with 20g of graphene oxide (the mass ratio of the zinc oxide to the graphene oxide is 4:1), dispersing into 5000g of water, sealing in a hydrothermal kettle, and reacting at 150 +/-5 ℃ for about 12 hours;
(2) adding 5000g of hydrazine hydrate into the system subjected to the step (1), and carrying out reduction reaction at the temperature of 60 +/-2 ℃ for about 2 hours;
(3) and (3) freezing and drying at the temperature of-50 ℃ to obtain a solid product, namely the graphene coated zinc oxide compound.
The graphene-coated zinc oxide obtained in the embodiment has a three-dimensional network structure, the graphene forms a three-dimensional gel network, and zinc oxide particles with the size of 10 nm-50 μm are coated inside graphene laminas with the thickness of 0.5-10 nm and the plane size of 500 nm-50 μm.
Example 2
A graphene-coated zinc oxide composite material is prepared by the following steps:
(1) dispersing 0.5g of graphene oxide in 1000g of water, dispersing 20g of zinc oxide obtained by a calcination method in 200g of water, slowly adding a zinc oxide aqueous solution into the graphene oxide aqueous solution, and stirring at room temperature to perform coprecipitation for 3 hours;
(2) adding 500g of hydrazine hydrate into the system obtained in the step (1), and carrying out reduction reaction at the temperature of 60 +/-2 ℃ for about 2 hours;
(3) and (3) freezing and drying at the temperature of-50 ℃ to obtain a solid product, namely the graphene coated zinc oxide compound.
Different from example 1, the graphene-coated zinc oxide is prepared by a coprecipitation method, and the morphology of the graphene-coated zinc oxide is represented by a scanning electron microscope and is shown in fig. 1, the obtained graphene-coated zinc oxide composite material is formed by completely coating a thin and flexible graphene sheet on the surface of zinc oxide particles with the size of 10nm to 50 μm, and the zinc oxide particles are uniformly distributed. Zinc oxide also achieves the formation of a composite with graphene without the addition of an additive, but the coating effect is not as good as with the addition of an additive.
The reversible charge-discharge curve of the full cell composed of the material of the present example is shown in fig. 2.
Example 3
A graphene-coated zinc oxide composite material is prepared by the following steps:
(1) dispersing 0.5g of graphene in 1000g of water, dispersing 20g of zinc oxide obtained by a calcination method in 200g of water, slowly adding a zinc oxide aqueous solution into the graphene oxide aqueous solution, and stirring at room temperature to perform coprecipitation for 3 hours;
(2) and (3) freezing and drying at the temperature of-50 ℃ to obtain a solid product, namely the graphene coated zinc oxide compound.
Different from the embodiment 2, the graphene is adopted as a raw material, the graphene-coated zinc oxide is prepared by a coprecipitation method, the step of chemically reducing the graphene oxide is not needed, the obtained graphene-coated zinc oxide composite material is formed by completely coating a thin and flexible graphene sheet layer on the surface of zinc oxide particles with the size of 10 nm-50 microns, and the zinc oxide particles are uniformly distributed.
Example 4
A graphene-coated zinc oxide composite material is prepared by the following steps:
(1) dispersing 20g of zinc oxide obtained by a calcination method in 200g of water, adding 20g of aminopropyltrimethoxysilane, and stirring at room temperature for 24 hours;
(2) dispersing 0.5g of graphene oxide in 1000g of water, slowly adding the system obtained in the step (1) into a graphene oxide aqueous solution, and stirring at room temperature to perform coprecipitation for 3 hours;
(3) adding 500g of hydrazine hydrate into the system obtained in the step (1), and carrying out reduction reaction at the temperature of 60 +/-2 ℃ for about 2 hours;
(4) and (3) freezing and drying at the temperature of-50 ℃ to obtain a solid product, namely the graphene coated zinc oxide compound.
The graphene-coated zinc oxide composite material obtained in the embodiment has a graphene-coated zinc oxide structure, thin and flexible graphene sheets completely coat the surfaces of zinc oxide particles with the size of 10 nm-50 mu m, and the zinc oxide particles are uniformly distributed.
Example 5
A graphene-coated zinc oxide composite material is prepared by the following steps:
(1) dispersing 20g of zinc oxide (prepared in a laboratory and with the particle size of 10 nm-1 mu m) obtained by a coprecipitation method in 200g of water, adding 20g of SDS, and stirring for 24 hours at room temperature;
(2) dispersing 0.5g of graphene oxide in 1000g of water, slowly adding the system obtained in the step (1) into a graphene oxide aqueous solution, and stirring at room temperature to perform coprecipitation for 3 hours;
(3) adding 500g of hydrazine hydrate into the system obtained in the step (1), and carrying out reduction reaction at the temperature of 60 +/-2 ℃ for about 2 hours;
(4) and (3) freezing and drying at the temperature of minus 50 ℃ to obtain a solid product, namely the graphene zinc oxide compound.
The graphene-coated zinc oxide composite material obtained in the embodiment has a graphene-coated zinc oxide structure, thin and flexible graphene sheets completely coat the surfaces of zinc oxide particles with the size of 10 nm-50 mu m, and the zinc oxide particles are uniformly distributed.
Example 6
A graphene-coated zinc oxide composite material is prepared by the following steps:
(1) dispersing 0.5g of graphene oxide in 1000g of water, dispersing 40g of zinc nitrate in 200g of water, slowly adding the zinc nitrate aqueous solution into the graphene oxide aqueous solution, and stirring at room temperature to perform coprecipitation for 3 hours;
(2) adding 500g of hydrazine hydrate into the system obtained in the step (1), and carrying out reduction reaction at the temperature of 60 +/-2 ℃ for about 2 hours;
(3) freeze-drying at-50 deg.C to obtain solid product;
(4) and (4) calcining the solid product obtained in the step (3) in a tubular furnace with nitrogen as a protective atmosphere at 500 ℃ for 2 hours to obtain the graphene coated zinc oxide composite material.
The graphene-coated zinc oxide composite material obtained in the embodiment is characterized by using a scanning electron microscope, and as shown in fig. 3, the obtained composite material has a graphene-coated zinc oxide structure, a thin and flexible graphene sheet layer completely coats the surface of zinc oxide particles with the size of 10nm to 200nm, and the zinc oxide particles are uniformly distributed. It was confirmed to have a ZnO structure by X-ray diffraction analysis as shown in FIG. 4.
Example 7
A graphene-coated zinc oxide composite material is prepared by the following steps:
(1) mixing 30g of zinc-aluminum hydrotalcite and 20g of graphene oxide, dispersing the mixture into 5000g of water, sealing the mixture in a hydrothermal kettle, and reacting at 150 +/-5 ℃ for about 12 hours;
(2) adding 5000g of hydrazine hydrate into the product system obtained in the step (1), and carrying out reduction reaction at the temperature of 60 +/-2 ℃ for about 2 hours;
(3) freeze drying at-50 deg.C to obtain solid product.
(4) And (4) calcining the solid product obtained in the step (3) in a tubular furnace with nitrogen as a protective atmosphere at 500 ℃ for 2 hours to obtain the graphene coated zinc oxide composite material.
The graphene-coated zinc oxide obtained in the embodiment has a three-dimensional network structure, the graphene forms a three-dimensional gel network, and zinc oxide particles with the size of 10 nm-50 μm are coated inside graphene laminas with the thickness of 0.5-10 nm and the plane size of 500 nm-50 μm.
Example 8
A graphene-coated zinc oxide composite material is prepared by the following steps:
(1) dispersing 0.5g of graphene oxide in 1000g of water, dispersing 40g of zinc acetate in 200g of water, slowly adding the aqueous solution of zinc acetate into the aqueous solution of graphene oxide, and stirring at room temperature to perform coprecipitation for 3 hours;
(2) adding 500g of hydrazine hydrate into the system obtained in the step (1), and carrying out reduction reaction at the temperature of 60 +/-2 ℃ for about 2 hours;
(3) freeze-drying at-50 deg.C to obtain solid product;
(4) and (4) calcining the solid product obtained in the step (3) in a tubular furnace with nitrogen as a protective atmosphere at 500 ℃ for 2 hours to obtain the graphene coated zinc oxide composite material.
The graphene-coated zinc oxide composite material obtained in the embodiment has a graphene-coated zinc oxide structure, thin and flexible graphene sheets completely coat the surfaces of zinc oxide particles with the size of 10 nm-50 mu m, and the zinc oxide particles are uniformly distributed.
Cycle performance test
The zinc-based battery negative working electrode is prepared by the following steps:
(1) coating a graphene-coated zinc oxide composite material, a binder PTFE and acetylene black according to the weight ratio of 8: 1: 1, mixing uniformly, preparing into paste with deionized water, and uniformly coating on a brass net;
(2) drying in a vacuum oven at 80 ℃ for 12 hours;
(3) and cutting the brass net coated with the graphene-coated zinc oxide composite material into wafers to manufacture the working electrodes.
The electrochemical performance of the electrode material was tested as follows:
(1) the simulated cell adopts a button type CR2032 system, wherein the positive electrode is spherical Ni (OH)2。
(2) Reversible capacity, coulombic efficiency and cycle performance of the electrode material are tested and analyzed by constant current charging and discharging in experiments. The charging and discharging system is as follows: voltage range: 1.0-1.9V; the number of cycles is generally from 1 to 3000.
The cycle charge and discharge characteristics of the full cell composed of the materials of examples 1 to 8 are shown in Table 1.
Table 1: examples 1-8 Charge and discharge Properties of the materials
Aiming at the defects of poor conductivity and poor cycle performance of zinc oxide, the invention finally obtains the negative electrode material for the rechargeable zinc-based battery with ultrahigh capacity, ultrahigh rate performance and super good cycle performance by controlling the preparation method and the preparation conditions. The method has very important significance for promoting the development of the high-performance zinc-based battery, solving the problem of energy shortage and the like.
The above examples are only illustrative of the specific embodiments of the present invention, and are not intended to limit the scope of the present invention, and those skilled in the art can make various modifications and changes based on the prior art, and various changes and modifications made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention are intended to fall within the scope of the present invention defined by the claims.
Claims (3)
1. The negative electrode material for the zinc-based battery is characterized in that the negative electrode material is of a structure that zinc oxide particles are coated by graphene laminas, and the mass percentage of zinc oxide in the negative electrode material is 60-95%; the thickness of the graphene sheet layer is 0.5-10 nm, and the plane size of the graphene is 500 nm-50 mu m;
the preparation method of the anode material comprises the following steps:
(1) dispersing 20g of zinc oxide in water, adding 20g of additive, and stirring for 24 hours; dispersing 0.5g of graphene oxide in water, slowly adding a zinc oxide solution into an aqueous solution of the graphene oxide, and stirring at room temperature to perform coprecipitation for 3 hours, wherein the additive is selected from aminopropyltriethoxysilane or SDS;
(2) after a dispersion system is formed in the step (1), adding hydrazine hydrate into the dispersion system to perform a reduction reaction, wherein the temperature of the reduction reaction is 60 +/-2 ℃;
(3) and (3) drying the product system in the step (2) by adopting freeze drying at the temperature of-50 ℃.
2. A battery comprising the negative electrode material for a zinc-based battery of claim 1.
3. The battery of claim 2, wherein the negative electrode of the battery is manufactured by a method comprising: mixing a negative electrode material, a binder and a conductive agent, and coating the mixture on a current collector; the positive electrode of the battery is nickel hydroxide.
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| CN108807961A (en) * | 2018-06-06 | 2018-11-13 | 上海电力学院 | A kind of zinc-base cell negative electrode material and preparation method thereof |
| CN113611828B (en) * | 2021-07-16 | 2023-10-24 | 山东合泰新能源有限公司 | Zinc oxide composite material, preparation method, negative electrode zinc paste and zinc-nickel storage battery |
| CN113745520B (en) * | 2021-09-05 | 2022-12-13 | 浙江大学 | Preparation method and application of zinc cathode material for inhibiting zinc dendrites |
| CN116425189B (en) * | 2022-08-29 | 2024-05-10 | 河南师范大学 | ZnO@ZnS@C composite negative electrode material for zinc-nickel secondary battery and preparation method and application thereof |
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| CN105702922A (en) * | 2016-01-22 | 2016-06-22 | 浙江极力动力新能源有限公司 | Zinc oxide modified graphene negative electrode paste of lithium ion battery and preparation method of negative electrode paste |
| CN106025251A (en) * | 2016-07-28 | 2016-10-12 | 新乡市超力新能源有限公司 | Preparation method of negative electrode material of zinc and nickel battery and slurry mixing method of negative electrode of zinc and nickel battery |
| CN106654303A (en) * | 2016-10-14 | 2017-05-10 | 济南大学 | ZnO-NiO/rGO composite material with efficient electrocatalytic oxygen reduction performance |
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| CN105702922A (en) * | 2016-01-22 | 2016-06-22 | 浙江极力动力新能源有限公司 | Zinc oxide modified graphene negative electrode paste of lithium ion battery and preparation method of negative electrode paste |
| CN106025251A (en) * | 2016-07-28 | 2016-10-12 | 新乡市超力新能源有限公司 | Preparation method of negative electrode material of zinc and nickel battery and slurry mixing method of negative electrode of zinc and nickel battery |
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Effective date of registration: 20210308 Address after: 453000 the southeast corner of the intersection of national highway 107 and Deyuan road in Xinxiang City, Henan Province passes through A1B and A1C of Filter Industrial Park in high tech Zone Patentee after: Henan Chaoli New Energy Co.,Ltd. Address before: 100191 No. 37, Haidian District, Beijing, Xueyuan Road Patentee before: BEIHANG University |
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