CN110336015B - Preparation method of carbon-coated tin and tin-iron alloy lithium ion battery cathode material - Google Patents
Preparation method of carbon-coated tin and tin-iron alloy lithium ion battery cathode material Download PDFInfo
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Abstract
The invention belongs to the technical field of electrode materials, and provides a preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material, which comprises the following steps: s1, adding crystalline stannic chloride, ferrous sulfate, polyvinylpyrrolidone and hydrazine hydrate into an alkaline deionized water solution to obtain a reaction solution, heating the reaction solution under the protection of inert gas for reaction, and then centrifugally washing to obtain the iron stannate oxide nanoparticles; s2, adding the iron hydroxystannate oxide nanoparticles obtained in the step S1, a carbon source and tris (hydroxymethyl) aminomethane into water, uniformly mixing, centrifuging, washing and drying to obtain iron hydroxystannate coated by the carbon source; and S3, calcining the carbon source coated iron hydroxyl stannate oxide obtained in the step S2 at 500-750 ℃ for 2-6 h in a hydrogen atmosphere to obtain the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material. By adopting the technical scheme, the problems of long preparation period and complex process of the preparation method of the carbon-coated tin and tin-iron alloy nano composite material in the prior art are solved.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and relates to a preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material.
Background
With the development of science and technology and the improvement of the living standard of people's material culture, people have more and more large demand on energy storage devices and have more and more high requirements on the performance of the energy storage devices. Particularly, with the development of space technology and the demand of military equipment, the emergence of a large number of industrial, civil and medical portable electronic products caused by the rapid development of information and microelectronic industry, the development and popularization of new energy electric automobiles and the enhancement of environmental protection consciousness, people have more urgent demands on batteries which are small in size, light in weight, high in energy, safe, reliable, pollution-free and capable of being repeatedly charged and used. Lithium ion batteries have received much attention from people because of their advantages of high energy density, working voltage (3V), no memory effect, long cycle life, no pollution, light weight, small self-discharge, etc.
The lithium ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and a shell, wherein the current commercialized negative electrode material is graphite, but the lithium storage capacity of the lithium ion battery is only 372mAh/g, and the lithium ion battery is more and more difficult to meet the needs of people. The search for new anode materials has important commercial value. The traditional preparation method of the carbon-coated alloy nano composite material as the lithium ion battery cathode material mainly comprises a pyrolysis method, a chemical vapor phase method, a deposition method, a laser candle burning method, a solvothermal method, an organogel carbonization method and an arc discharge method, and has a plurality of deep analysis and recognition on the synthesis mechanism; most of them use high temperature to evaporate carbon and then deposit it, and some of them use pyrolysis of organic matter or use long-term low-temperature carbonization of organic matter in liquid phase. These methods have problems, such as: the method is provided with special requirements, the process is complex, and the overall reaction time is long. In addition, a layer of carbon material is generally coated on the surface of the prepared nano-particles by the process, and the prior art cannot prepare the carbon-coated nano-particles with uniform shapes and tissues by one-step reaction.
In conclusion, the preparation method of the carbon-coated tin and tin-iron alloy nanocomposite material in the prior art has the problems of long preparation period, complex process and the like, and an effective solution is still lacking.
Disclosure of Invention
The invention provides a preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material, and solves the problems of long preparation period and complex process of the preparation method of the carbon-coated tin and tin-iron alloy nano composite material in the prior art.
The technical scheme of the invention is realized as follows:
a preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material comprises the following steps:
s1, adding crystalline stannic chloride, ferrous sulfate, polyvinylpyrrolidone and hydrazine hydrate into an alkaline deionized water solution to obtain a reaction solution, heating the reaction solution under the protection of inert gas for reaction, and then centrifugally washing to obtain the iron stannate oxide nanoparticles;
s2, adding the iron hydroxystannate oxide nanoparticles obtained in the step S1, a carbon source and tris (hydroxymethyl) aminomethane into water, uniformly mixing, centrifuging, washing and drying to obtain iron hydroxystannate coated by the carbon source;
and S3, calcining the carbon source coated iron hydroxyl stannate oxide obtained in the step S2 at 500-750 ℃ for 2-6 h in a hydrogen atmosphere to obtain the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material.
As a further technical scheme, in the alkaline deionized water solution in the step S1, the alkaline substance is strong alkali or weak alkali, and the pH value is 10-13.
As a further technical scheme, the strong base is sodium hydroxide or potassium hydroxide, and the weak base is sodium carbonate or ammonia water.
As a further technical scheme, in the step S1, the mass ratio of the polyvinylpyrrolidone to the ferrous sulfate to the crystalline stannic chloride is 1: 0.5-2: 1-3, wherein the volume of hydrazine hydrate accounts for 0.05-0.2% of the total volume of the reaction solution.
As a further technical scheme, in the heating reaction of the step S1, the heating temperature is 20-80 ℃, and the reaction time is 6-24 hours.
As a further technical scheme, in the step S2, the mass ratio of the iron oxytolunate nanoparticles to the carbon source to the tris (hydroxymethyl) aminomethane is 1-3: 1: 0.5 to 2.
As a further technical scheme, in the step S2, the carbon source is one or more of dopamine hydrochloride, glucose, sucrose and resorcinol formaldehyde resin.
As a further technical scheme, in the step S3, the calcining temperature is 600-700 ℃, and the calcining time is 5-6 h.
The carbon-coated tin and tin-iron alloy lithium ion battery cathode material is prepared by the preparation method of the carbon-coated tin and tin-iron alloy lithium ion battery cathode material, and the particle size of the carbon-coated tin and tin-iron alloy lithium ion battery cathode material is 100-300 nm.
The working principle and the beneficial effects of the invention are as follows:
1. in the invention, the carbon-coated tin and tin-iron alloy lithium ion battery cathode material is prepared by adopting tin tetrachloride and ferrous sulfate as main materials, the raw materials are wide in source, low in price and easy to obtain, meanwhile, the preparation process is simple, the target product can be obtained only by three steps of reaction, and the problems of long preparation period and complex process of the preparation method of the carbon-coated tin and tin-iron alloy nano composite material in the prior art are effectively solved.
2. According to the invention, the carbon-coated tin and tin-iron alloy are applied to the lithium ion battery cathode material, compared with graphite serving as the cathode specific capacity 372mAh/g, the carbon-coated tin and tin-iron alloy lithium ion battery cathode material is greatly improved, the particle size of the prepared carbon-coated tin and tin-iron alloy lithium ion battery cathode material is 100-300 nm, the battery capacity after 50 times of charge and discharge cycles is stabilized at 509mAh/g under the current density of 500mA/g, the particle size distribution is uniform, the cycling stability is good, and the carbon-coated tin and tin-iron alloy lithium ion battery cathode material is suitable for being popularized and used.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a Transmission Electron Microscope (TEM) image of a carbon-coated tin and tin-iron alloy lithium ion battery anode material prepared in example 1 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the carbon-coated tin and tin-iron alloy lithium ion battery cathode material prepared in example 2 of the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) image of the negative electrode material of the carbon-coated tin and tin-iron alloy lithium ion battery prepared in example 3 of the present invention;
FIG. 4 is a Transmission Electron Microscope (TEM) image of the negative electrode material of the carbon-coated tin and tin-iron alloy lithium ion battery prepared in example 4 of the present invention;
FIG. 5 is a Transmission Electron Microscope (TEM) image of the negative electrode material of the carbon-coated tin and tin-iron alloy lithium ion battery prepared in example 5 of the present invention;
FIG. 6 is a Transmission Electron Microscope (TEM) image of the negative electrode material of the carbon-coated tin and tin-iron alloy lithium ion battery prepared in example 6 of the present invention;
FIG. 7 is a Transmission Electron Microscope (TEM) image of the negative electrode material of the carbon-coated tin and tin-iron alloy lithium ion battery prepared in example 7 of the present invention;
FIG. 8 is an X-ray diffraction pattern of the negative electrode material of the carbon-coated tin and tin-iron alloy lithium ion battery prepared in example 1 of the present invention;
in the figure:
the diffraction peak of Sn was shown in the site,. diamond-solid was shown in the site of FeSn2The diffraction peak of FeO is expressed in part;
FIG. 9 is a graph showing the cycling stability of the negative electrode material of the carbon-coated tin and tin-iron alloy lithium ion battery prepared in example 1 under a current density of 500 mA/g;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material comprises the following steps:
s1, weighing 0.8g of polyvinylpyrrolidone, 1.3g of crystallized stannic chloride and 0.56g of sodium hydroxide, dissolving in 140ml of deionized water, adding 200ul of hydrazine hydrate, stirring uniformly, and adding a sodium hydroxide solution to adjust the pH value to 12.5. Dissolving 1.0g of ferrous sulfate in 60ml of deionized water, adding the solution into the system to obtain a reaction solution, heating the reaction solution in a water bath under the protection of inert gas to 35 ℃ for reaction for 12 hours, centrifuging, washing and drying to obtain iron stannate oxide nanoparticles;
s2, weighing 0.36g of tris (hydroxymethyl) aminomethane and dissolving the tris (hydroxymethyl) aminomethane in 300ml of deionized water, then weighing 0.3g of the iron hydroxystannate nano particles obtained in the step S1 and 0.27g of dopamine hydrochloride, respectively adding the weighed materials into the solution, stirring the solution for 24 hours, centrifuging, washing and drying the solution to obtain a carbon source coated iron hydroxystannate;
and S3, placing the carbon source coated hydroxyl stannic acid iron oxide obtained in the step S2 in a tubular furnace, and calcining for 6 hours at 650 ℃ in a hydrogen atmosphere to obtain the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material.
Example 2
A preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material comprises the following steps:
s1, weighing 0.7g of polyvinylpyrrolidone, 1.3g of crystallized stannic chloride and 0.56g of sodium hydroxide, dissolving in 140ml of deionized water, adding 200ul of hydrazine hydrate, stirring uniformly, and adding a sodium hydroxide solution to adjust the pH value to 12.5. Dissolving 1.0g of ferrous sulfate in 60ml of deionized water, adding the solution into the system to obtain a reaction solution, heating the reaction solution in a water bath under the protection of inert gas to 35 ℃ for reaction for 12 hours, centrifuging, washing and drying to obtain iron stannate oxide nanoparticles;
s2, weighing 0.36g of tris (hydroxymethyl) aminomethane and dissolving the tris (hydroxymethyl) aminomethane in 300ml of deionized water, then weighing 0.3g of the iron hydroxystannate nano particles obtained in the step S1 and 0.27g of dopamine hydrochloride, respectively adding the weighed materials into the solution, stirring the solution for 24 hours, centrifuging, washing and drying the solution to obtain a carbon source coated iron hydroxystannate;
and S3, placing the carbon source coated hydroxyl stannic acid iron oxide obtained in the step S2 in a tubular furnace, and calcining for 6 hours at 750 ℃ in a hydrogen atmosphere to obtain the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material.
Example 3
A preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material comprises the following steps:
s1, weighing 0.7g of polyvinylpyrrolidone, 1.3g of crystallized stannic chloride and 0.56g of sodium hydroxide, dissolving in 140ml of deionized water, adding 200ul of hydrazine hydrate, stirring uniformly, and adding a sodium hydroxide solution to adjust the pH value to 12.5. Dissolving 1.0g of ferrous sulfate in 60ml of deionized water, adding the solution into the system to obtain a reaction solution, heating the reaction solution to 30 ℃ in a water bath under the protection of inert gas for reaction for 12 hours, centrifuging, washing and drying to obtain iron stannate oxide nanoparticles;
s2, weighing 0.3g of tris (hydroxymethyl) aminomethane and dissolving the tris (hydroxymethyl) aminomethane in 300ml of deionized water, then weighing 0.3g of the iron hydroxystannate nano particles obtained in the step S1 and 0.27g of dopamine hydrochloride, respectively adding the weighed materials into the solution, stirring the solution for 24 hours, centrifuging, washing and drying the solution to obtain a carbon source coated iron hydroxystannate;
and S3, placing the carbon source coated hydroxyl-stannic acid iron oxide obtained in the step S2 in a tubular furnace, and calcining for 6 hours at 700 ℃ in a hydrogen atmosphere to obtain the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material.
Example 4
A preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material comprises the following steps:
s1, weighing 0.8g of polyvinylpyrrolidone, 1.3g of crystallized stannic chloride and 0.56g of sodium hydroxide, dissolving in 140ml of deionized water, adding 200ul of hydrazine hydrate, stirring uniformly, and adding a sodium hydroxide solution to adjust the pH value to 12.5. Dissolving 1.0g of ferrous sulfate in 60ml of deionized water, adding the solution into the system to obtain a reaction solution, heating the reaction solution in a water bath under the protection of inert gas to 35 ℃ for reaction for 12 hours, centrifuging, washing and drying to obtain iron stannate oxide nanoparticles;
s2, weighing 0.36g of tris (hydroxymethyl) aminomethane and dissolving the tris (hydroxymethyl) aminomethane in 300ml of deionized water, then weighing 0.3g of the iron hydroxystannate nano particles obtained in the step S1 and 0.27g of dopamine hydrochloride, respectively adding the weighed materials into the solution, stirring the solution for 24 hours, centrifuging, washing and drying the solution to obtain a carbon source coated iron hydroxystannate;
and S3, placing the carbon source coated hydroxyl-tin oxide acid iron obtained in the step S2 in a tubular furnace, and calcining for 5 hours at 600 ℃ in a hydrogen atmosphere to obtain the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material.
Example 5
A preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material comprises the following steps:
s1, weighing 0.7g of polyvinylpyrrolidone, 2.1g of crystallized stannic chloride and 0.56g of sodium hydroxide, dissolving in 140ml of deionized water, adding 100ul of hydrazine hydrate, stirring uniformly, and adding a sodium carbonate solution to adjust the pH value to 10. Dissolving 1.4g of ferrous sulfate in 60ml of deionized water, adding the solution into the system to obtain a reaction solution, heating the reaction solution in a water bath under the protection of inert gas to 35 ℃ for reaction for 12 hours, centrifuging, washing and drying to obtain iron stannate oxide nanoparticles;
s2, weighing 0.15g of tris (hydroxymethyl) aminomethane, dissolving in 300ml of deionized water, weighing 0.3g of the iron hydroxystannate nano particles obtained in the step S1, weighing 0.3g of dopamine hydrochloride, respectively adding into the solution, stirring for 24 hours, centrifuging, washing, and drying to obtain a carbon source coated iron hydroxystannate;
and S3, placing the carbon source coated hydroxyl-stannic acid iron oxide obtained in the step S2 in a tubular furnace, and calcining for 6 hours at 550 ℃ in a hydrogen atmosphere to obtain the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material.
Example 6
A preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material comprises the following steps:
s1, weighing 0.8g of polyvinylpyrrolidone, 0.8g of crystallized stannic chloride and 0.56g of sodium hydroxide, dissolving in 140ml of deionized water, adding 400ul of hydrazine hydrate, stirring uniformly, and adding a sodium hydroxide solution to adjust the pH value to 12.5. Dissolving 0.4g of ferrous sulfate in 60ml of deionized water, adding the solution into the system to obtain a reaction solution, heating the reaction solution in a water bath under the protection of inert gas to 20 ℃ for reaction for 24 hours, centrifuging, washing and drying to obtain iron hydroxystannate oxide nanoparticles;
s2, weighing 0.6g of tris (hydroxymethyl) aminomethane, dissolving the tris (hydroxymethyl) aminomethane in 300ml of deionized water, weighing 0.9g of the iron hydroxystannate oxide nanoparticles obtained in the step S1, weighing 0.3g of resorcinol formaldehyde resin, respectively adding the resorcinol formaldehyde resin into the solution, stirring for 24 hours, centrifuging, washing, and drying to obtain a carbon source coated iron hydroxystannate;
and S3, placing the carbon source coated hydroxyl-stannic acid iron oxide obtained in the step S2 in a tubular furnace, and calcining for 6 hours at 500 ℃ in a hydrogen atmosphere to obtain the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material.
Example 7
A preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material comprises the following steps:
s1, weighing 0.7g of polyvinylpyrrolidone, 1.3g of crystallized stannic chloride and 0.56g of sodium hydroxide, dissolving in 140ml of deionized water, adding 200ul of hydrazine hydrate, stirring uniformly, and adding an ammonia water solution to adjust the pH value to 12.5. Dissolving 1.0g of ferrous sulfate in 60ml of deionized water, adding the solution into the system to obtain a reaction solution, heating the reaction solution in a water bath under the protection of inert gas to 80 ℃ for reaction for 6 hours, centrifuging, washing and drying to obtain iron stannate oxide nanoparticles;
s2, weighing 0.3g of tris (hydroxymethyl) aminomethane and dissolving the tris (hydroxymethyl) aminomethane in 300ml of deionized water, weighing 0.3g of the iron stannate oxide nanoparticles obtained in the step S1, weighing 0.27g of glucose, adding the glucose and the iron stannate oxide nanoparticles into the solution respectively, stirring the solution for 24 hours, centrifuging, washing and drying the solution to obtain iron stannate oxide coated with a carbon source;
and S3, placing the carbon source coated hydroxyl stannic acid iron oxide obtained in the step S2 in a tubular furnace, and calcining for 2 hours at 750 ℃ in a hydrogen atmosphere to obtain the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material.
TEM images of the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode materials prepared in examples 1 to 7 are shown in FIGS. 1 to 7, and it can be seen from the TEM images that the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode materials prepared in examples 1 to 7 have uniform particle size distribution and particle size of 100 to 300 nm.
The X-ray diffraction pattern of the lithium ion battery cathode material with carbon-coated tin and tin-iron alloy particles prepared in example 1 is shown in FIG. 8, and Sn and FeSn which can be respectively seen from the X-ray diffraction pattern2And diffraction peaks of FeO, X-ray diffraction tests were also performed on the carbon-coated tin and tin-iron alloy particle lithium ion battery anode materials prepared in examples 2 to 7, and the test results are the same as those in FIG. 8, so that the X-ray diffraction tests are omitted.
The cycle stability test result of the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material prepared in example 1 is shown in fig. 9, and it can be seen from the figure that the battery capacity of the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material prepared in example 1 is stabilized at 509mAh/g after 50 charge and discharge cycles at a current density of 500mA/g, which indicates that the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material prepared in example 1 of the present invention has a good cycle stability, and the cycle stability test is also performed on the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode materials prepared in examples 2 to 7, and the test result is the same as that in fig. 9, so the test is omitted.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a carbon-coated tin and tin-iron alloy lithium ion battery cathode material is characterized by comprising the following steps:
s1, adding crystalline tin tetrachloride, ferrous sulfate, polyvinylpyrrolidone and hydrazine hydrate into an alkaline deionized water solution to obtain a reaction solution, heating the reaction solution under the protection of inert gas for reaction, and then centrifugally washing to obtain the hydroxyl stannic acid ferric oxide nanoparticles, wherein the mass ratio of the polyvinylpyrrolidone to the ferrous sulfate to the crystalline tin tetrachloride is 1: 0.5-2: 1-3, wherein the volume of hydrazine hydrate accounts for 0.05% -0.2% of the total volume of the reaction liquid;
s2, adding the iron hydroxystannate oxide nanoparticles obtained in the step S1, a carbon source and tris (hydroxymethyl) aminomethane into water, uniformly mixing, centrifuging, washing and drying to obtain a carbon source coated iron hydroxystannate oxide, wherein the mass ratio of the iron hydroxystannate oxide nanoparticles to the carbon source to the tris (hydroxymethyl) aminomethane is 1-3: 1: 0.5 to 2;
and S3, calcining the carbon source coated iron hydroxyl stannate oxide obtained in the step S2 at 500-750 ℃ for 2-6 h in a hydrogen atmosphere to obtain the carbon-coated tin and tin-iron alloy particle lithium ion battery cathode material.
2. The method for preparing the carbon-coated tin and tin-iron alloy lithium ion battery anode material as claimed in claim 1, wherein in the step S1, the alkaline substance is strong alkali or weak alkali in the alkaline deionized water solution, and the pH value is 10-13.
3. The method for preparing the carbon-coated tin and tin-iron alloy lithium ion battery negative electrode material as claimed in claim 2, wherein the strong base is sodium hydroxide or potassium hydroxide, and the weak base is sodium carbonate or ammonia water.
4. The method for preparing the carbon-coated tin and tin-iron alloy lithium ion battery anode material as claimed in claim 1, wherein in the heating reaction of step S1, the heating temperature is 20-80 ℃ and the reaction time is 6-24 h.
5. The method for preparing the carbon-coated tin and tin-iron alloy lithium ion battery anode material as claimed in claim 1, wherein the carbon source in step S2 is one or more of dopamine hydrochloride, glucose, sucrose and resorcinol-formaldehyde resin.
6. The method for preparing the carbon-coated tin and tin-iron alloy lithium ion battery anode material as claimed in claim 1, wherein the calcination temperature in step S3 is 600-700 ℃, and the calcination time is 5-6 h.
7. The carbon-coated tin and tin-iron alloy lithium ion battery negative electrode material obtained by the preparation method of the carbon-coated tin and tin-iron alloy lithium ion battery negative electrode material according to any one of claims 1 to 6, wherein the particle size of the carbon-coated tin and tin-iron alloy lithium ion battery negative electrode material is 100 to 300 nm.
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| CN102208638B (en) * | 2011-04-26 | 2013-10-23 | 浙江大学 | High-capacity lithium ion battery cathode composite material and preparation method thereof |
| CN103435105B (en) * | 2013-08-07 | 2016-03-23 | 浙江凯恩电池有限公司 | A kind of ferriferous oxide/carbon composition lithium ion battery cathode material and its preparation method and application |
| CN103887484B (en) * | 2014-02-20 | 2017-01-11 | 安徽师范大学 | Iron tin oxide nano material, preparation method of material, positive electrode of lithium ion battery and lithium ion battery |
| CN105762354B (en) * | 2016-05-17 | 2018-04-13 | 安徽师范大学 | A kind of flower-shaped ferric oxide nano-material and preparation method thereof, negative electrode of lithium ion battery and lithium ion battery |
| CN107321359B (en) * | 2017-07-24 | 2019-04-05 | 福州大学 | A kind of hydroxyl stannate iron/graphene composite photocatalyst and preparation method thereof |
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2019
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