CN112447954A - Graphene-modified ferrate material and preparation method and application thereof - Google Patents
Graphene-modified ferrate material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112447954A CN112447954A CN201910827413.XA CN201910827413A CN112447954A CN 112447954 A CN112447954 A CN 112447954A CN 201910827413 A CN201910827413 A CN 201910827413A CN 112447954 A CN112447954 A CN 112447954A
- Authority
- CN
- China
- Prior art keywords
- ferrate
- graphene
- graphite oxide
- feo
- crg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The invention relates to a graphene modified ferrate material and a preparation method and application thereof, wherein the method comprises the following steps: preparing strong acid graphite oxide, washing the strong acid graphite oxide for multiple times by using a mixed solution containing nitrogen methyl pyrrolidone and absolute ethyl alcohol to obtain neutral graphite oxide, and uniformly dispersing the neutral graphite oxide by using water to obtain a graphite oxide water dispersion solution; reducing graphite oxide in the graphite oxide aqueous dispersion into chemically reduced graphene under an ultrasonic-assisted hydrothermal condition by using ascorbic acid as a reducing agent, and then performing suction filtration and drying to obtain the chemically reduced graphene; and (3) preparing the ferrate material modified by the graphene from ferrate and chemically reduced graphene ethanol dispersion liquid by a codeposition method. According to the invention, the chemical reduction graphene is coated on the surface of ferrate by a codeposition method, so that the stability of ferrate in a humid environment and a saturated KOH solution is obviously improved, and the actual discharge performance of an alkaline super-iron battery consisting of the ferrate and Zn under various conditions is obviously improved.
Description
Technical Field
The invention belongs to the technical field of super-iron batteries, and particularly relates to a graphene modified ferrate material as well as a preparation method and application thereof.
Background
With the increasing demand for green chemical energy and almost exhausted electrode materials, ferrate compounds have a broad development prospect as battery cathode materials. In 1999, litch used ferrate (MFeO) 4 ) Replacement of MnO in alkaline Zinc-manganese cell as cathode Material 2 Cathode and this new cell is named "super-iron cell", MFeO 4 The discharge products of the/Zn battery are ZnO, water and Fe which do not pollute the environment 2 O 3 With alkaline MnO 2 MFeO vs. Zn and lead acid batteries 4 the/Zn battery is a green and pollution-free sustainable energy source and is praised as a new generation of 'green battery'. However, despite its potential advantages, ferrate is limited by chemical instability. Ferrate is very unstable and easy to decompose in aqueous solution or humid environment; and oxygen can be released immediately under acidic condition and is decomposed slowly in neutral or weak alkaline solution. The wide application of the super-iron battery is limited due to poor stability of ferrate. Thus, maintaining a stable and sustained discharge is critical to improving the electrochemical performance of ferrate batteries.
In order to improve the stability of ferrate cathode, zirconium chloride has been proposed(ZrCl 4 ) Zirconium dioxide (ZrO) 2 ) Yttrium oxide-zirconium dioxide (Y) 2 O 3 -ZrO 2 ) Phthalocyanine (H) 2 PC) and the like for potassium ferrate (K) 2 FeO 4 ) Coating is performed to improve the discharge performance of potassium ferrate cathode, but when these substances are used as coating materials, MFeO 4 The capacitance of the/Zn battery still has the problems of insignificant increase and the like.
Graphene is a carbon material emerging in the 21 st century, and is widely concerned by people due to excellent electrical, thermal, mechanical and optical properties, and the like, and particularly applied to the field of electrochemical energy storage. At present, graphene Oxide (GO) and Chemically Reduced Graphene (CRG) have been successfully applied to lithium ion batteries, supercapacitors and lithium-air batteries, and good results have been obtained. However, no reports are available about using Chemically Reduced Graphene (CRG) to coat ferrate as a cathode to improve the stability and discharge performance of a super-iron battery.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a graphene modified ferrate material and a preparation method and application thereof. According to the method, chemically Reduced Graphene (CRG) is used as a coating material and coated on the surface of ferrate by a codeposition method, so that the stability of ferrate in a humid environment and a saturated KOH solution is obviously improved, and the actual discharge performance of an alkaline super-iron battery consisting of the ferrate and Zn under various conditions is improved.
In order to achieve the above object, the present invention provides, in a first aspect, a method for preparing a graphene-modified ferrate material, the method comprising the steps of:
(1) Preparing strong-acid graphite oxide, washing the strong-acid graphite oxide for multiple times by using a mixed solution containing nitrogen methyl pyrrolidone and absolute ethyl alcohol to obtain neutral graphite oxide, and then uniformly dispersing the neutral graphite oxide by using water to obtain a graphite oxide water dispersion liquid;
(2) Reducing graphite oxide in the graphite oxide aqueous dispersion into chemically reduced graphene under an ultrasonic-assisted hydrothermal condition by using ascorbic acid as a reducing agent, and then sequentially performing suction filtration and drying to obtain the chemically reduced graphene;
(3) Preparing chemical reduction graphene ethanol dispersion liquid by using the chemical reduction graphene obtained in the step (2), and preparing the graphene modified ferrate material with ferrate coated by the chemical reduction graphene by using a codeposition method through ferrate and the chemical reduction graphene ethanol dispersion liquid.
Preferably, the ferrate is one or more of potassium ferrate, sodium ferrate, barium ferrate, lithium ferrate, cesium ferrate, silver ferrate and strontium ferrate; preferably, the ferrate is potassium ferrate.
Preferably, in step (1), the volume ratio of the strongly acidic graphite oxide to the N-methylpyrrolidone and the anhydrous ethanol contained in the mixed solution is 1.
Preferably, the method further comprises: and co-depositing the graphene-modified ferrate material and the chemical reduction graphene ethanol dispersion liquid for multiple times to obtain graphene-modified ferrate materials with different chemical reduction graphene coating amounts.
Preferably, the mass ratio of ferrate contained in the graphene-modified ferrate material to reduced graphene is 100: (0.8-5.2).
Preferably, the concentration of graphite oxide contained in the graphite oxide aqueous dispersion is 0.05 to 0.2mg/L.
Preferably, the concentration of the chemically reduced graphene contained in the chemically reduced graphene ethanol dispersion liquid is 0.05 to 0.12mg/mL.
Preferably, the hydrothermal temperature is 24 to 60 ℃.
In a second aspect, the present invention provides a graphene-modified ferrate material prepared by the preparation method according to the first aspect of the present invention.
In a third aspect, the present invention provides a graphene-modified ferrate material prepared by the preparation method of the first aspect of the present invention, and the application of the graphene-modified ferrate material as a cathode material in a super-iron battery.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) According to the method, the strong-acid graphite oxide is innovatively cleaned by using the mixed solution of N-methyl pyrrolidone (NMP) and absolute ethyl alcohol, and the graphite oxide with the pH value not more than 1 can be converted into neutral after 6-7 times of cleaning, so that the efficiency of preparing the neutral graphite oxide is effectively improved.
(2) According to the method, chemically Reduced Graphene (CRG) is used as a coating material and coated on the surface of ferrate by a codeposition method, so that the stability of ferrate in a humid environment and a saturated KOH solution is obviously improved, and the actual discharge performance of an alkaline super-iron battery consisting of the ferrate and Zn under various conditions is improved.
(3) After 60 days, the prepared graphene modified ferrate material has CRG (Crg-coated glass) type K in a humid environment 2 FeO 4 The purity of (5 times) was 46.7%, which is higher than that of uncoated K 2 FeO 4 The height is 33.9 percent; CRG-coated K in saturated KOH solution 2 FeO 4 The purity of (5 times) was 75.9% as compared with that of uncoated K 2 FeO 4 Higher by 25.6%; when the graphene-modified ferrate material prepared by the invention is applied as a cathode material of a super-iron battery, the CRG coated K 2 FeO 4 (5 times) the ratio K of actual capacitance and active component utilization rate of alkaline super-iron battery composed of Zn at 1775 omega 2 FeO 4 The higher ratio is 22.9% and 22.8%, respectively, compared with MnO 2 The higher ratios were 33.4% and 15.9%, respectively.
Drawings
Fig. 1 is an infrared spectrum (FTIR spectrum) of neutral Graphite Oxide (GO) and Chemically Reduced Graphene (CRG) in example 1 of the present invention. In the figure, a is an FTIR spectrum of CRG, and b is an FTIR spectrum of GO.
Fig. 2 is an X-ray photoelectron spectroscopy (XPS) spectrum of neutral Graphite Oxide (GO) and Chemically Reduced Graphene (CRG) in example 1 of the present invention. In the figure, a is the XPS spectrum of GO and b is the XPS spectrum of CRG.
Fig. 3 is an X-ray diffraction spectrum (XRD spectrum) of graphite powder, neutral Graphite Oxide (GO), and Chemically Reduced Graphene (CRG) in example 1 of the present invention. In the figure, a is an XRD spectrogram of CRG, b is an XRD spectrogram of GO, and c is an XRD spectrogram of graphite powder.
FIG. 4 shows K in example 1 of the present invention 2 FeO 4 And CRG coated form K 2 FeO 4 Photographs (3 times) and SEM images. In the figure, a and c respectively represent K 2 FeO 4 In the figure, b and d represent CRG-coated K, respectively 2 FeO 4 Photographs (3 times) and SEM images.
FIG. 5 shows K in example 2 of the present invention 2 FeO 4 And CRG coated type K 2 FeO 4 (3 times) purity in different environments versus time. In which a denotes K 2 FeO 4 + dry air, b denotes CRG-coated type K 2 FeO 4 (3 times) + saturated KOH solution, c represents K 2 FeO 4 + saturated KOH solution, d denotes CRG-coated K 2 FeO 4 (3 times) + moist air, e denotes K 2 FeO 4 Purity in + moist air versus time. In the figure, the abscissa Time represents Time in days (day) and the ordinate Purity (%) represents Purity in%.
FIG. 6 shows K in example 2 of the present invention 2 FeO 4 CRG coated K 2 FeO 4 (1, 3 and 5) purity in humid air as a function of time. In the figure, a, b, c and d respectively represent K 2 FeO 4 CRG coated K 2 FeO 4 (1 time) CRG-coated K 2 FeO 4 (3 times) CRG-coated K 2 FeO 4 (5 times) purity in humid air versus time.
FIG. 7 CRG-coated type K in example 3 of the present invention 2 FeO 4 Graph of discharge performance at 1775 Ω. In which a denotes K 2 FeO 4 B represents a CRG-coated type K 2 FeO 4 (1 st) discharge Performance Curve, c represents CRG-coated K 2 FeO 4 (3 times) discharge Performance Curve, d represents CRG-coated K 2 FeO 4 Discharge Performance Curve (5 times), e represents MnO 2 Discharge performance curve of (d). In the figure, the abscissa Sepcific Capacity represents the actual discharge amount in mAh, and the ordinate Voltage represents the Voltage in V.
FIG. 8 shows a CRG-coated type K in example 3 of the present invention 2 FeO 4 Discharge performance plots at 200 Ω and 20 Ω. In the figure, a represents a CRG-coated type K 2 FeO 4 (5 times) discharge Performance Curve at 200. Omega. B represents CRG-coated K 2 FeO 4 Discharge performance curve at 20 Ω (5 times).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of a graphene modified ferrate material in a first aspect, which comprises the following steps:
(1) Preparing strong acid graphite oxide (graphite oxide with pH not more than 1), washing the strong acid graphite oxide for multiple times by using a mixed solution containing N-methyl pyrrolidone (NMP) and absolute ethyl alcohol to obtain neutral graphite oxide, and then uniformly dispersing the neutral graphite oxide by using water to obtain a graphite oxide water dispersion liquid (GO dispersion liquid); in the invention, the graphite oxide is graphene oxide, and the graphite oxide water dispersion liquid refers to a dispersion liquid which takes neutral graphite oxide as a dispersoid and water as a dispersion medium; in the present invention, the strongly acidic graphite oxide can be produced, for example, by the Hummers method using graphite powder as a raw material; in the present invention, the neutral graphite oxide is a hydrous neutral graphite oxide (hydrous graphite oxide) which is not dried after washing, because the inventors have found through a large number of experiments that a large number of oxygen-containing functional groups having poor stability on the surface of graphite oxide are rapidly decomposed during drying, causing difficulty in completely dispersing solid graphite oxide in water, and the mass concentration of the dispersion can be significantly improved by using hydrous graphite oxide as a dispersoid. In the present invention, the specific steps of washing with the mixed solution containing the nitrogen methyl pyrrolidone and the anhydrous ethanol may be, for example: adding a mixed solution of NMP and absolute ethyl alcohol into the strongly acidic graphite oxide according to a certain volume ratio, stirring for 5 minutes, standing for 20 minutes, carrying out vacuum filtration on the mixed solution which is placed for 20 minutes, stirring and dispersing the obtained filter cake into 100mL of distilled water, and separating graphite oxide with weakened acidity by centrifugation (8000 r/min,15 min); and finally, repeatedly treating the graphite oxide with reduced acidity by using NMP, absolute ethyl alcohol and deionized water until the pH =7 or so to obtain the neutral graphite oxide.
(2) Reducing Graphite Oxide (GO) in the graphite oxide water dispersion liquid (GO dispersion liquid) obtained in the step (1) into Chemically Reduced Graphene (CRG) by using ascorbic acid (reduced ascorbic acid, L-AA) as a reducing agent under an ultrasonic-assisted hydrothermal condition, and then sequentially performing suction filtration and drying to obtain the Chemically Reduced Graphene (CRG); specifically, for example, the aqueous graphite oxide dispersion is placed in a water bath, L-AA is added, the reaction is carried out under the assistance of ultrasound until a pure black CRG aqueous dispersion is obtained, then the CRG aqueous dispersion is filtered in vacuum to obtain a black filter cake, and finally the black filter cake is placed in a 50 ℃ vacuum drying oven to be dried for 12 hours, so that the black film-like solid CRG can be obtained.
(3) Preparing a chemical reduction graphene ethanol dispersion solution (CRG ethanol dispersion solution) by using the chemical reduction graphene obtained in the step (2), and preparing the graphene modified ferrate material of which ferrate is coated by the chemical reduction graphene by using a codeposition method through ferrate and the chemical reduction graphene ethanol dispersion solution; in the present invention, in particular, for example, ferrate powder such as potassium ferrate powder (K) 2 FeO 4 ) Adding into CRG ethanol dispersion, rapidly stirring to make potassium ferrate suspend in the dispersion, stopping stirring after 20min, and standing for 10min; then removing the residual ethanol from the solid-liquid mixture by vacuum filtration, and then placing the filter residue in a vacuum drying oven at 50 ℃ for 2h to remove the residual ethanol, thus obtaining the K with the surface coated by CRG 2 FeO 4 And gently flicked to remove excess CRG. In the present invention, the chemically reduced graphene ethanol dispersion refers to a dispersion in which chemically reduced graphene is used as a dispersoid and ethanol (e.g., absolute ethanol) is used as a dispersion medium; in the present invention, when the ferrate is K 2 FeO 4 In the meantime, the ferrate material modified by graphene is also recorded as CRG-coated K 2 FeO 4 。
As is well known, the well-established preparation processes for preparing graphite oxide include the Brodie method, the Standenmaier method and the Hummers method, among which the Hummers method, which is relatively safe and simple, is widely used, but the Hummers method produces strongly acidic graphite oxide, which cannot be used as it is, and thus it is necessary to remove acidic substances adsorbed thereto. The acid removal method in the prior art mainly comprises centrifugal washing, suction filtration washing or infiltration, but the centrifugal washing and the infiltration waste a large amount of water and time and cannot be treated in a large scale. In addition, during the continuous filtration and washing process, the flaky graphite oxide will expand in volume due to water adsorption, and the expanded graphite oxide will block the micropores in the filtration membrane, so it is very difficult to remove the acidic substances completely by vacuum filtration. Compared with the traditional filtration water washing, permeation and centrifugal water washing, the method for washing the acidic graphite oxide by using the mixed solution of the N-methyl pyrrolidone and the absolute ethyl alcohol is used for washing the acidic graphite oxide for 6-7 times, so that the pH value of the acidic graphite oxide can be increased from no more than 1 to 6.5-7.
In addition, the method takes Chemically Reduced Graphene (CRG) as a coating material, and coats the surface of the ferrate by a codeposition method, so that the stability of the ferrate in a humid environment and a saturated KOH solution is obviously improved, and the actual discharge performance of the alkaline super-iron battery consisting of the ferrate and Zn under various conditions is improved.
According to some preferred embodiments, the ferrate is potassium ferrate (K) 2 FeO 4 ) Sodium ferrate (Na) 2 FeO 4 ) Barium ferrate (BaFeO) 4 ) Lithium ferrate (Li) 2 FeO 4 ) Cesium ferrate (Cs) 2 FeO 4 ) Silver ferrate (Ag) 2 FeO 4 ) Strontium ferrate (SrFeO) 4 ) One or more of; preferably, the ferrate is potassium ferrate; in the present invention, the potassium ferrate can be produced, for example, by a hypochlorite oxidation method (one-step method).
According to some preferred embodiments, in step (1), the volume ratio of the strongly acidic graphite oxide to the N-methylpyrrolidone and anhydrous ethanol contained in the mixed solution is 1.
According to some preferred embodiments, the method further comprises: and co-depositing the graphene-modified ferrate material and the chemical reduction graphene ethanol dispersion liquid for multiple times to obtain graphene-modified ferrate materials with different chemical reduction graphene coating amounts. In the invention, specifically, for example, the graphene-modified ferrate material powder is added into a newly prepared CRG ethanol dispersion liquid, and is rapidly stirred so that the graphene-modified ferrate material is suspended in the dispersion liquid, and after 20min, the stirring is stopped, and then the mixture is still for 10min; then removing the residual ethanol from the solid-liquid mixture through vacuum filtration, and then placing the filter residue in a vacuum drying oven at 50 ℃ for 2 hours to remove the residual ethanol, thus obtaining the graphene-modified ferrate material coated with chemically reduced graphene for the second time; and repeating the step for multiple times of codeposition to obtain the graphene-modified ferrate material which is repeatedly coated by the chemically reduced graphene, and thus obtaining various graphene-modified ferrate materials with different chemically reduced graphene coating amounts.In the present invention, CRG is coated on K 2 FeO 4 The reason for the surface may be that in a very low polarity ethanol solution, the surface has negatively charged K 2 FeO 4 Will attract CRG with positive charges on the surface to coat the CRG on the K 2 FeO 4 Surface, co-deposition phenomenon occurs; when CRG is in the coated form K 2 FeO 4 When the CRG is put into a new CRG dispersion again, the balance of the dispersion is lost, and the CRG originally dispersed is again coated with the CRG-coated K 2 FeO 4 Agglomeration occurred, so treatment K was repeated using a CRG ethanol dispersion 2 FeO 4 K with different CRG coating amounts can be obtained 2 FeO 4 。
According to some preferred embodiments, the graphene-modified ferrate material comprises ferrate and chemically-reduced graphene in a mass ratio of 100: (0.8-5.2).
According to some preferred embodiments, the aqueous graphite oxide dispersion contains graphite oxide at a concentration of 0.05 to 0.2mg/L (e.g. 0.05, 0.1, 0.15 or 0.2 mg/L), preferably 0.15mg/L.
According to some preferred embodiments, the chemically reduced graphene contained in the chemically reduced graphene ethanol dispersion liquid has a concentration of 0.05 to 0.12mg/mL (e.g., 0.05, 0.1, or 0.12 mg/mL), preferably 0.1mg/mL.
According to some preferred embodiments, the hydrothermal temperature (reaction temperature under hydrothermal conditions) is from 24 to 60 ℃ (e.g., 24 ℃,36 ℃, 48 ℃, or 60 ℃), preferably 36 ℃. The inventor finds that the reduction speed of reduced ascorbic acid (L-AA) on Graphite Oxide (GO) can be obviously improved by increasing the hydrothermal temperature, and the chemical reaction rates at 36 ℃, 48 ℃ and 60 ℃ are about 2 times, 3 times and 3 times of those at 24 ℃. However, after the reaction temperature exceeds 36 ℃, GO with gradually reduced oxygen content can agglomerate in water to form amorphous carbon, and the agglomeration phenomenon is more obvious when the reaction temperature is higher. The inventor finds that the reduction under the ultrasonic-assisted hydrothermal condition can effectively prevent amorphous carbon from occurring in Chemically Reduced Graphene (CRG) aqueous dispersion prepared at 36 ℃, and can also remarkably improve the reduction speed by more than 15 times at 24 ℃. However, when the reaction temperature exceeds 48 ℃, the ability of ultrasonic assistance to prevent amorphous carbon formation is insufficient. Thus, the inventors found that in the present invention, the optimal reaction conditions for preparing CRG were to subject the aqueous GO dispersion to 36 ℃ ultrasound-assisted reduction for 2h.
In a second aspect, the present invention provides a graphene-modified ferrate material prepared by the preparation method according to the first aspect of the present invention.
In a third aspect, the present invention provides a graphene-modified ferrate material prepared by the preparation method of the first aspect of the present invention, and the application of the graphene-modified ferrate material as a cathode material in a super-iron battery.
The present invention will be further described with reference to the following examples. These examples are merely illustrative of preferred embodiments of the present invention and the scope of the present invention should not be construed as being limited to these examples.
Example 1: preparation of graphene-modified ferrate material
(1) Adding a two-system mixed solution of NMP and absolute ethyl alcohol into the strongly acidic graphite oxide according to a volume ratio of the strongly acidic graphite oxide to the NMP to ethanol =1 = 2; vacuum filtering the mixed solution for 20min, dispersing the obtained filter cake in 100mL of distilled water under stirring, and centrifuging (8000 r/min,15 min) to separate graphite oxide with reduced acidity; finally, repeatedly treating the graphite oxide with reduced acidity with NMP, absolute ethanol and deionized water (the volume ratio of each time of the graphite oxide with reduced acidity to NMP: ethanol is 1; finally, uniformly dispersing the neutral graphite oxide by using water to obtain a graphite oxide water dispersion liquid (GO dispersion liquid) with the mass concentration of the graphite oxide being 0.15 mg/mL; the strongly acidic graphite oxide is prepared by taking graphite powder as a raw material through a Hummers method.
(2) Putting the graphite oxide water dispersion liquid with the concentration of 0.15mg/mL into a water bath kettle at 36 ℃, adding ascorbic acid L-AA to enable the concentration of the L-AA in the dispersion liquid to be 30mg/L, reacting for 2 hours under the assistance of ultrasound until pure black CRG water dispersion liquid is obtained, then carrying out vacuum filtration on the CRG water dispersion liquid to obtain a black filter cake, finally putting the black filter cake into a vacuum drying oven at 50 ℃ for drying for 12 hours to obtain black film-shaped solid CRG, and grinding the black film-shaped solid CRG into powder.
(3) Preparing 20mL of chemical reduction graphene ethanol dispersion liquid (CRG ethanol dispersion liquid) with the mass concentration of CRG being 0.1 mg/mL; 100mg of ground potassium ferrate (K) was uniformly mixed 2 FeO 4 ) Adding the powder to the CRG ethanol dispersion, and rapidly stirring to obtain K 2 FeO 4 Suspending in the dispersion, stopping stirring after 20min, and standing for 10min; then removing the residual ethanol from the solid-liquid mixture by vacuum filtration, and then placing the filter residue in a vacuum drying oven at 50 ℃ for 2h to remove the residual ethanol, thus obtaining the K with the surface coated by CRG 2 FeO 4 And gently flicked to remove excess CRG. K to be coated 1 time with GO 2 FeO 4 The coating steps are repeated to obtain K with different CRG coating amounts 2 FeO 4 (graphene-modified ferrate materials with different amounts of chemically reduced graphene coating). The mass data of the coated CRG are shown in table 1. Wherein, K 2 FeO 4 For preparing K with purity of 94.7% by hypochlorite oxidation method 2 FeO 4 And (4) crystals.
Table 1: k is 2 FeO 4 And CRG coated type K 2 FeO 4 Quality data of
| Number of coating | K 2 FeO 4 (mg) | CRG-coated K 2 FeO 4 (mg) | Percentage of |
| 1 | 100 | 100.8 | 0.8％ |
| 3 | 100 | 102.7 | 2.7％ |
| 5 | 100 | 105.2 | 5.2％ |
In this example, the chemical and crystal structures of the resulting CRG were characterized by infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD): in comparison with graphite oxide, part of the oxygen-containing peak in the FTIR spectrum of CRG is apparently disappeared, for example, as shown in FIG. 1, CRG is at 1730cm -1 (telescopic vibration of O-C = O or C = O), 1224cm -1 (stretching vibration of O-C-O) 1051cm -1 (C-O stretching vibration) and 3391cm -1 The disappearance and attenuation of the absorption peak at the position (-stretching vibration of OH bond) can prove that L-AA can effectively reduce graphite oxide to CRG, but at 1388cm -1 A newly appeared C-OH absorption peak indicates that a small amount of oxygen-containing functional groups are remained in the CRG; compared with graphite oxide, the strength and area of an oxygen-containing peak in an XPS spectrum are obviously reduced, for example, as shown in figure 2, it is proved that L-AA can effectively cause C-O/C-O-C in GO to undergo a ring opening reaction, and then GO is reduced into CRG; the XRD pattern is remarkably enhanced in interlayer spacing and conductivity as compared with graphite oxide, for example, as shown in fig. 3, the characteristic diffraction peak of graphite oxide appears at 2 θ =11.4 ° and at an interlayer spacing of 0.794nm, passing throughAfter the reduction of the L-AA, the characteristic diffraction peak of the graphite oxide has disappeared, and a new diffraction peak appears at 2 θ =24.5 ° (pitch of 0.37 nm), and the position of the new diffraction peak is similar to the position of the characteristic (002) diffraction peak of the graphite (2 θ =26.1 °, pitch of 0.34 nm), but the peak is flat, and the interlayer spacing of the CRG is smaller than that of the graphite oxide but larger than the theoretical interlayer spacing value (0.335 nm) of the graphene, which indicates that the L-AA removes most of the oxygen-containing functional groups in the CRG, but a small amount of the oxygen-containing functional groups remain between the interlayers of the CRG, and the plane electron conjugated system of the CRG is reconstructed to a certain extent.
In this embodiment, for K 2 FeO 4 And CRG coated type K 2 FeO 4 Scanning electron microscopy characterization (SEM characterization) was performed (3 times) as shown in fig. 4: phase contrast K 2 FeO 4 CRG coated K 2 FeO 4 (3 times), in CRG ethanol dispersion, can be at K by codeposition 2 FeO 4 The CRG coating layer is formed on the surface to a certain thickness and appears in appearance as the crystal particles with metallic luster (fig. 4 a) are transformed into dark black particles with larger volume (fig. 4 b), and the appearance under SEM is irregular lumps (balls) piled up together.
Example 2: CRG-coated pair K 2 FeO 4 Effect test on stability
Using K in example 1 2 FeO 4 And CRG coated type K 2 FeO 4 The experiment was performed (3 times): mixing three parts of K 2 FeO 4 Respectively placing in dry air at normal temperature, in humid air environment (humid environment) and saturated KOH solution environment, and coating two portions of CRG with K 2 FeO 4 (3 times) placing in a humid air environment and a saturated KOH solution environment respectively, and researching K 2 FeO 4 CRG coated K 2 FeO 4 (3 times) the change in purity with time in different environments, the results are shown in FIG. 5.
As can be seen from fig. 5: in dry air at normal temperature, K 2 FeO 4 The purity of (D) is reduced by only 1.1% within 60d, which indicates that K is 2 FeO 4 Is stable in dry air. However, will K 2 FeO 4 And CRG bagCoating type K 2 FeO 4 After being placed in a humid environment for 60 days (3 times), the purity is greatly reduced to 12.8 percent and 40.8 percent respectively, and is reduced to 81.9 percent and 53.9 percent respectively. In addition, to simulate the environment of a super-ferrous battery, K is shifted 2 FeO 4 Adding saturated KOH solution, K 2 FeO 4 The purity of the crystal is reduced to 50.3 percent and 44.4 percent from the initial 94.7 percent within 60 days, while the CRG coated K 2 FeO 4 The purity (3 times) is reduced to 75.9% in a small way and 18.8% in a small way. CRG-coated K in humid and saturated KOH environments 2 FeO 4 The change in purity of (3) always lies at K 2 FeO 4 In the above, it is shown that the CRG coating can significantly improve K 2 FeO 4 Is probably due to the coating at K 2 FeO 4 The large amount of CRG on the surface has excellent hydrophobic property, can isolate most of water outside and further prevent K 2 FeO 4 A rapid large scale hydrolysis reaction occurs.
This example further investigated the number of CRG coatings versus K 2 FeO 4 The effect of stability in a humid environment, as shown in fig. 6: CRG coated K after 60d placement 2 FeO 4 The purity of (5 times) is about 46.7% in comparison with K 2 FeO 4 Higher by 33.9% (difference), but with CRG-coated K 2 FeO 4 The purity of the product (3 times) is similar; this indicates that the more times the coating was performed, the CRG-coated form K 2 FeO 4 The better the stability of (b), but too much coating becomes less effective. Although after CRG coating, K 2 FeO 4 The purity of (A) is still obviously reduced in a humid environment, which shows that CRG is in K 2 FeO 4 The coating formed on the surface can only prevent the water in the electrolyte from largely soaking in for a certain time, but compared with the prior K coated by other materials 2 FeO 4 Already significantly improve K 2 FeO 4 Stability in a humid environment.
In the invention, the purity of the potassium ferrate solid sample is analyzed by a chromite method, and the calculation formula of the potassium ferrate purity is as follows:
in the formula: the purity of the P-potassium ferrate; v-iron ammonium sulfate solution Fe (NH) consumed 4 ) 2 (SO 4 ) 2 Volume (mL); N-Fe (NH) 4 ) 2 (SO 4 ) 2 Equivalent concentration; m W -K 2 FeO 4 Molecular weight =198.04; M-K 2 FeO 4 Sample quality or CRG coated K 2 FeO 4 Sample mass.
Example 3: CRG-coated K 2 FeO 4 Discharge performance test experiment under constant temperature and constant resistance
Will K 2 FeO 4 Or CRG coated K 2 FeO 4 The material is mixed with acetylene black and rolled into a sheet to be used as a cathode, zn foil is used as an anode, saturated potassium hydroxide is used as electrolyte, a glass fiber diaphragm is used as a battery diaphragm to form the CR2032 type button battery, and the concrete raw material proportion is as follows: k 2 FeO 4 Or CRG coated K 2 FeO 4 : acetylene black: zn =100mg:10mg:200mg.
The discharge performance curve and the active ingredient utilization rate of the CR2032 type button battery under the load of constant resistance 1775 omega are tested, and the test method comprises the following steps: discharging the battery under a constant resistance, collecting time, voltage and current data through a battery test system, and performing piecewise fitting on time and current curves by using origin software, wherein a fitting model is a polynomial of degree 2; calculating the area of the graph formed by the time-current curve and the abscissa through fixed integral, namely the actual discharge capacity (actual capacitance), drawing an actual capacitance-voltage curve, namely a discharge performance curve, and K 2 FeO 4 The calculation formula of the effective utilization rate of the active ingredients is as follows:
in the formula: a: effective benefit of active ingredientsA rate of utilization; c:100mg K 2 FeO 4 Or CRG coated K 2 FeO 4 Actual discharge capacity; 40.6:100mg of K with a purity of 100% 2 FeO 4 The theoretical capacitance of (1); 94.7%: k used 2 FeO 4 The purity of (2).
K obtained in this example 2 FeO 4 CRG coated K 2 FeO 4 (n coats) (n =1, 3 and 5) and MnO 2 The discharge performance curve of the/Zn coin cell under the load of 1775 omega is shown in figure 7, and the discharge performance curve and the active ingredient utilization rate data are shown in table 2.
Table 2: CRG-coated K 2 FeO 4 Discharge efficiency and active ingredient utilization of the discharge at 1775 Ω.
| Cathode material | Actual discharge capacity (mAh) | Active ingredient utilization ratio (%) |
| K 2 FeO 4 | 25.6 | 66.5 |
| CRG coated K 2 FeO 4 (1 time) | 29.5 | 76.6 |
| CRG-coated K 2 FeO 4 (3 times) | 32.3 | 83.9 |
| CRG-coated K 2 FeO 4 (5 times) | 33.2 | 86.2 |
| MnO 2 | 22.1 | 72.5 |
Note: CRG-coated form K in Table 2 2 FeO 4 The CRG-coated K prepared in example 1 was used 2 FeO 4 (1 time) CRG-coated K 2 FeO 4 (3 times) and CRG-coated form K 2 FeO 4 (5 times) materials.
As can be seen from fig. 7 and table 2: when the cut-off voltage is 0.8V, 100mg K 2 FeO 4 The actual discharge capacity is about 25.6mAh, the starting and stopping voltage is 1.61V, the discharge plateau voltage is 1.56 +/-0.05V and the utilization rate of active ingredients is about 66.5 percent. And after CRG coating, K 2 FeO 4 The actual discharge amount of (a) significantly increases with the increase in the CRG coating amount. CRG coated K when n =5 2 FeO 4 The actual discharge capacity can reach 33.2mAh, the starting and stopping voltage is increased to 1.73V, the discharge platform is 1.57 +/-0.05V, and the utilization rate of active ingredients is up to 86.2%. In contrast to alkaline zinc-manganese cells, the cathode material of button cells was replaced by MnO 2 The experimental result shows that 100mg MnO is 2 The actual discharge capacity is about 22.1mAh, the starting and stopping voltage is 1.52V, the discharge platform is 1.28 +/-0.05V and the utilization rate of active substances is 72.5 percent. With CRG-coated K 2 FeO 4 (5 times) comparison, mnO 2 The ratio of the capacitance lower than that of (A) was 33.4%, the ratio of the discharge plateau voltage lower was 18.9% and the ratio of the active ingredient utilization lower was 15.9%, indicating that CRG-coated K 2 FeO 4 (5 times) to MnO 2 The electrochemical performance is more excellent.
This example further investigated load pairs of CRG-coated K 2 FeO 4 The effect of discharge performance of CRG coated K is tested 2 FeO 4 Discharge performance curves and active ingredient utilization rates at 200 Ω and 20 Ω (5 times), and the results are shown in fig. 8 and table 3.
Table 3: CRG coated K 2 FeO 4 Discharge efficiency and active ingredient utilization rate of the discharge at 200 Ω and 20 Ω (5 times).
As can be seen from FIG. 8 and Table 3, CRG cladding type K is obtained under loads of 200. Omega. And 20. Omega 2 FeO 4 (5 times) and MnO 2 The actual discharge amount of the discharge electrode is obviously reduced, and the discharge platform is obviously reduced. When the load is 200 omega, the CRG cladding type K 2 FeO 4 The actual discharge capacity (5 times) was reduced by 12.3% to 1775 Ω, the discharge plateau voltage was reduced by 8.2%, and the active ingredient utilization rate was reduced by 12.4%. When the load is 20 omega, the CRG coated K 2 FeO 4 The actual discharge capacity (5 times), the discharge plateau voltage and the active ingredient utilization rate were further reduced. MnO for simultaneous comparison 2 The actual discharge capacity, discharge plateau voltage and active ingredient utilization ratio under 200 omega and 20 omega are higher than that of CRG cladding type K 2 FeO 4 (5 times) lower. It can be seen that even under heavy-load discharge, CRG-coated K 2 FeO 4 The discharge performance of the (5 times) is also higher than that of MnO 2 。
Finally, the description is as follows: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the embodiments can be modified, or some technical features can be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention in its aspects.
Claims (10)
1. A preparation method of a graphene-modified ferrate material is characterized by comprising the following steps of:
(1) Preparing strong-acid graphite oxide, washing the strong-acid graphite oxide for multiple times by using a mixed solution containing nitrogen methyl pyrrolidone and absolute ethyl alcohol to obtain neutral graphite oxide, and then uniformly dispersing the neutral graphite oxide by using water to obtain a graphite oxide water dispersion liquid;
(2) Reducing graphite oxide in the graphite oxide aqueous dispersion into chemically reduced graphene under an ultrasonic-assisted hydrothermal condition by using ascorbic acid as a reducing agent, and then sequentially performing suction filtration and drying to obtain the chemically reduced graphene;
(3) Preparing chemical reduction graphene ethanol dispersion liquid by using the chemical reduction graphene obtained in the step (2), and preparing the graphene modified ferrate material with ferrate coated by the chemical reduction graphene by using a codeposition method through ferrate and the chemical reduction graphene ethanol dispersion liquid.
2. The method of claim 1, wherein:
the ferrate is one or more of potassium ferrate, sodium ferrate, barium ferrate, lithium ferrate, cesium ferrate, silver ferrate and strontium ferrate;
preferably, the ferrate is potassium ferrate.
3. The method of claim 1, wherein:
in step (1), the volume ratio of the strongly acidic graphite oxide to the N-methylpyrrolidone and absolute ethanol contained in the mixed solution is 1.
4. The method of manufacturing according to claim 1, further comprising:
and co-depositing the graphene-modified ferrate material and the chemical reduction graphene ethanol dispersion liquid for multiple times to obtain graphene-modified ferrate materials with different chemical reduction graphene coating amounts.
5. The production method according to any one of claims 1 to 4, characterized in that:
the mass ratio of ferrate contained in the graphene-modified ferrate material to chemically reduced graphene is 100: (0.8-5.2).
6. The production method according to any one of claims 1 to 4, characterized in that:
the concentration of the graphite oxide contained in the graphite oxide water dispersion liquid is 0.05-0.2 mg/L.
7. The production method according to any one of claims 1 to 4, characterized in that:
the concentration of the chemically reduced graphene contained in the chemically reduced graphene ethanol dispersion liquid is 0.05-0.12 mg/mL.
8. The production method according to any one of claims 1 to 4, characterized in that:
the hydrothermal temperature is 24-60 ℃.
9. The graphene-modified ferrate material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the graphene-modified ferrate material prepared by the preparation method of any one of claims 1 to 8 as a cathode material in a super-iron battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910827413.XA CN112447954B (en) | 2019-09-03 | 2019-09-03 | Graphene-modified ferrate material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910827413.XA CN112447954B (en) | 2019-09-03 | 2019-09-03 | Graphene-modified ferrate material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112447954A true CN112447954A (en) | 2021-03-05 |
| CN112447954B CN112447954B (en) | 2022-02-08 |
Family
ID=74735413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910827413.XA Expired - Fee Related CN112447954B (en) | 2019-09-03 | 2019-09-03 | Graphene-modified ferrate material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112447954B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115050947A (en) * | 2022-07-29 | 2022-09-13 | 湖北亿纬动力有限公司 | Modified ferrate cathode material, preparation method thereof and lithium ion battery |
| CN115513442A (en) * | 2022-11-04 | 2022-12-23 | 晖阳(贵州)新能源材料有限公司 | High-energy-density composite negative electrode material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145121A (en) * | 2013-03-19 | 2013-06-12 | 苏州格瑞丰纳米科技有限公司 | Preparation method of thin-layer graphene oxide material |
| JP2015150555A (en) * | 2014-02-13 | 2015-08-24 | ポステック アカデミー‐インダストリー ファウンデーション | Hydrogenation catalyst supporting inorganic nanoparticles thereon, method for producing the same, and method for hydrogenating biomass-derived hydrocarbon compound using hydrogenation catalyst |
| CN104868105A (en) * | 2015-04-15 | 2015-08-26 | 南京邮电大学 | Preparation method of three-dimensional graphene composite electrode material with high mechanical strength |
| CN105273114A (en) * | 2015-11-23 | 2016-01-27 | 复旦大学 | Method for preparing low oxidation degree graphene-modified polymethyl methacrylate (PMMA) composite material |
| CN107611365A (en) * | 2017-07-27 | 2018-01-19 | 华南理工大学 | Graphene and ferroferric oxide double-coated nano-silicon composite material, preparation method thereof and application thereof in lithium ion battery |
| CN109904400A (en) * | 2017-12-08 | 2019-06-18 | 中国石油化工股份有限公司 | A kind of molybdenum disulfide/three-dimensional graphene composite material |
| CN110164702A (en) * | 2018-01-23 | 2019-08-23 | 泰顺永庆电力技术有限公司 | A kind of lithium battery carbon/manganese dioxide composite material and its application |
-
2019
- 2019-09-03 CN CN201910827413.XA patent/CN112447954B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145121A (en) * | 2013-03-19 | 2013-06-12 | 苏州格瑞丰纳米科技有限公司 | Preparation method of thin-layer graphene oxide material |
| JP2015150555A (en) * | 2014-02-13 | 2015-08-24 | ポステック アカデミー‐インダストリー ファウンデーション | Hydrogenation catalyst supporting inorganic nanoparticles thereon, method for producing the same, and method for hydrogenating biomass-derived hydrocarbon compound using hydrogenation catalyst |
| CN104868105A (en) * | 2015-04-15 | 2015-08-26 | 南京邮电大学 | Preparation method of three-dimensional graphene composite electrode material with high mechanical strength |
| CN105273114A (en) * | 2015-11-23 | 2016-01-27 | 复旦大学 | Method for preparing low oxidation degree graphene-modified polymethyl methacrylate (PMMA) composite material |
| CN107611365A (en) * | 2017-07-27 | 2018-01-19 | 华南理工大学 | Graphene and ferroferric oxide double-coated nano-silicon composite material, preparation method thereof and application thereof in lithium ion battery |
| CN109904400A (en) * | 2017-12-08 | 2019-06-18 | 中国石油化工股份有限公司 | A kind of molybdenum disulfide/three-dimensional graphene composite material |
| CN110164702A (en) * | 2018-01-23 | 2019-08-23 | 泰顺永庆电力技术有限公司 | A kind of lithium battery carbon/manganese dioxide composite material and its application |
Non-Patent Citations (1)
| Title |
|---|
| 郭玉凤，等: "石墨烯包覆高铁酸钾复合材料的制备及其电化学性能研究", 《第30届全国化学与物理电源学术年会论文集》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115050947A (en) * | 2022-07-29 | 2022-09-13 | 湖北亿纬动力有限公司 | Modified ferrate cathode material, preparation method thereof and lithium ion battery |
| CN115513442A (en) * | 2022-11-04 | 2022-12-23 | 晖阳(贵州)新能源材料有限公司 | High-energy-density composite negative electrode material and preparation method thereof |
| CN115513442B (en) * | 2022-11-04 | 2023-10-27 | 晖阳(贵州)新能源材料有限公司 | High-energy-density composite anode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112447954B (en) | 2022-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2019019411A1 (en) | Lithium metal-skeletal carbon composite material with hydrophobic cladding layer and preparation method and use thereof | |
| CN112447954B (en) | Graphene-modified ferrate material and preparation method and application thereof | |
| CN102757040B (en) | Graphene-based hydrogel and preparation method thereof as well as preparation method and application of supercapacitor electrode taking graphene-based hydrogel as active material | |
| KR101406371B1 (en) | Metal or Metal oxide/Graphene self-assembly Nanocomposite of Three-dimensional structure and Method of preparing the same | |
| CN106410156B (en) | A kind of Si-C composite material, preparation method and its application | |
| Xu et al. | An interfacial coating with high corrosion resistance based on halloysite nanotubes for anode protection of zinc-ion batteries | |
| CN102532891A (en) | Graphene/polyaniline nano-fiber composite material and preparation method and application in super capacitor thereof | |
| Chen et al. | Controlling hydroxyl content of reduced graphene oxide for superior cathode performance of lithium sulfur batteries | |
| CN110391400B (en) | Preparation method of flexible self-supporting silicon/ultra-long titanium dioxide nanotube electrode | |
| CN116505099A (en) | Composite lithium supplementing material, preparation method and application thereof | |
| CN113745521B (en) | Preparation method and application of zinc electrode material capable of inhibiting self-discharge | |
| JP2022531997A (en) | Prelithiated negative electrodes, their fabrication methods, lithium-ion batteries containing prelithiated negative electrodes, and supercapacitors. | |
| CN113943022B (en) | Cobalt-based MOFs-derived hollow spherical Co9S8/Ni3S4 heterojunction material and preparation method and application thereof | |
| CN112864391A (en) | Preparation method and application of lead/reduced graphene oxide nanocomposite | |
| CN109860476B (en) | Titanium dioxide colloid modified diaphragm for lithium-sulfur battery, preparation method of diaphragm and lithium-sulfur battery | |
| CN114974916B (en) | Fibrous MXene-loaded NiCoS composite material and preparation method and application thereof | |
| WO2020045279A1 (en) | Electrolytic manganese dioxide, method for producing same, and use of same | |
| CN107275567A (en) | Positive pole, water system energy storage device and anode preparation method comprising the positive pole | |
| WO2018180208A1 (en) | Electrolytic manganese dioxide, method for manufacturing same, and application for same | |
| CN109686575A (en) | A kind of preparation method of tin oxide nano piece/polyaniline composite material | |
| CN112117136B (en) | GO-CS coated potassium ferrate material and preparation method and application thereof | |
| CN107293748A (en) | A kind of ZnMn2S4Nanoparticle, its preparation method and application | |
| CN112117447A (en) | Preparation process of composite lithium battery negative electrode material | |
| JP3353588B2 (en) | Method for producing manganese oxide for battery and battery | |
| Taguchi et al. | Discharge-Charge Property of Lead-Acid Battery Using Nano-Scale PbO2 as Cathode Active Material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220208 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |