CN109301198B - Nickel nanosheet array loaded zinc oxide composite electrode and preparation method thereof - Google Patents

Nickel nanosheet array loaded zinc oxide composite electrode and preparation method thereof Download PDF

Info

Publication number
CN109301198B
CN109301198B CN201811087345.XA CN201811087345A CN109301198B CN 109301198 B CN109301198 B CN 109301198B CN 201811087345 A CN201811087345 A CN 201811087345A CN 109301198 B CN109301198 B CN 109301198B
Authority
CN
China
Prior art keywords
nickel
zinc oxide
nanosheet array
composite electrode
electrode material
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.)
Active
Application number
CN201811087345.XA
Other languages
Chinese (zh)
Other versions
CN109301198A (en
Inventor
黄小华
吴建波
钟文武
申士杰
林燕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taizhou University
Original Assignee
Taizhou University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Taizhou University filed Critical Taizhou University
Priority to CN201811087345.XA priority Critical patent/CN109301198B/en
Publication of CN109301198A publication Critical patent/CN109301198A/en
Application granted granted Critical
Publication of CN109301198B publication Critical patent/CN109301198B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/364—Composites as mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/626—Metals
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 discloses a nickel nanosheet array loaded zinc oxide composite electrode material and a preparation method and application thereof. The method comprises the following steps: vertically growing a nickel oxyhydroxide (NiOOH) nanosheet array on a nickel foil substrate by using a chemical water bath deposition method; further depositing zinc oxide on the hydroxyl nickel oxide nanosheet array by using a radio frequency magnetron sputtering method; and (3) reducing the hydroxyl nickel oxide in the obtained composite material into metallic nickel by using hydrogen-argon mixed gas, and finally preparing the nickel nanosheet array loaded zinc oxide composite electrode material. When the material is used for a lithium ion battery cathode, the material has excellent electrochemical performance due to the composite effect between the nickel nanosheet array and the zinc oxide, and compared with the conventional zinc oxide cathode material, the reversible capacity, the first coulombic efficiency, the cycling stability and the high-rate performance of the material are greatly improved.

Description

Nickel nanosheet array loaded zinc oxide composite electrode and preparation method thereof
Technical Field
The invention relates to an electrode material of a lithium ion battery, in particular to a nickel nanosheet array loaded zinc oxide composite electrode material and a preparation method and application thereof.
Background
With the continuous exhaustion of fossil energy and the increasing severity of environmental pollution, the active development of new energy and the construction of low-carbon society have become strategic issues of major concern in all countries in the world. As a high-energy green secondary battery, a lithium ion battery has remarkable characteristics of high voltage, high capacity, high power, and long life, and has been commercially used on a large scale. In recent years, with the development of technology, new requirements are put on the energy density of lithium ion batteries, and the existing commercial graphite negative electrode materials are mature, the capacity of the graphite negative electrode materials is almost exerted to the limit, and the requirements are difficult to meet. Therefore, development of a novel, inexpensive, high-capacity lithium ion battery negative electrode material is urgently required.
In the lithium ion battery cathode material, zinc oxide is a high-capacity material, and the theoretical capacity of the zinc oxide is 988 mAh/g, which is much higher than that of a graphite material. It has the advantages of stable chemical property, easy preparation, low cost, etc. However, its low first coulombic efficiency, poor cycle stability and conductivity limits its practical application. Therefore, how to overcome these disadvantages is a key scientific problem that needs to be solved urgently when the lithium ion battery cathode material is applied.
Disclosure of Invention
The invention aims to provide a nickel nanosheet array loaded zinc oxide composite electrode material and a preparation method thereof.
A nickel nanosheet array loaded zinc oxide composite electrode material and a preparation method thereof comprise the following steps:
(1) vertically growing a hydroxyl nickel oxide nanosheet array on a nickel foil substrate by adopting a chemical water bath deposition method;
(2) further depositing zinc oxide on the nickel oxyhydroxide array obtained in the step (1) by adopting a video magnetron sputtering method to obtain a nickel oxyhydroxide nanosheet array loaded zinc oxide composite material;
(3) and (3) reducing the hydroxyl nickel oxide in the composite material obtained in the step (2) into metallic nickel by using hydrogen-argon mixed gas by adopting a reduction method, and finally obtaining the nickel nanosheet array loaded zinc oxide composite electrode material.
In the step (1), chemical water is usedThe method comprises the following steps of (1) vertically growing a hydroxyl nickel oxide nanosheet array on a nickel foil substrate by a bath deposition method, wherein the specific conditions are as follows: the reaction solution is a mixed solution of nickel sulfate and potassium persulfate, the concentration of nickel sulfate is 0.2-0.6 mol/L, the concentration of potassium persulfate is 0.05-0.1 mol/L, the size of the nickel foil substrate is (1 cm multiplied by 1 cm) ~ (5 cm multiplied by 5 cm), 5-15 mL of concentrated ammonia water is added to trigger the deposition reaction, and the reaction temperature is controlled to be 10-40oAnd C, the reaction time is 0.5-3 h.
In the step (2), depositing zinc oxide on the vertical hydroxyl nickel oxide nanosheet array obtained in the step (1) by using a radio frequency magnetron sputtering method, wherein the specific conditions are as follows: the target is zinc oxide ceramic, the distance between the sample table and the target is 15-25 cm, the working gas is high-purity argon, the pressure is 5-10 mTorr, the sputtering power is 50-100W, and the sputtering time is 2-12 hours.
In the step (3), a reduction method is adopted, hydrogen-argon mixed gas is used as a reduction atmosphere, nickel oxyhydroxide in the composite material obtained in the step (2) is reduced into metallic nickel, and finally the nickel nanosheet array zinc oxide-loaded composite electrode material is prepared, wherein the specific conditions are as follows: the hydrogen-argon mixed gas contains 5-10% of hydrogen by volume and the reduction temperature is 300-500%oAnd C, the reduction reaction time is 1-3 h.
In the nickel nanosheet array loaded zinc oxide composite electrode material, the array height is 0.5-3 mu m, and the surface density of nickel is 0.05-0.4 mg/cm2The surface density of the zinc oxide is 0.2-1.2 mg/cm2。
In the composite electrode material, the nickel nanosheet array and the zinc oxide active material have obvious composite effect, and the electrochemical performance of the composite electrode material can be obviously enhanced. Compared with the prior art, the method has the advantages of the following performances:
firstly, the nano nickel component in the electrode can generate reversible electrochemical conversion reaction with lithium oxide generated after zinc oxide is discharged for the first time (Ni + Li)2O ↔ NiO + 2Li), the utilization rate of the electrode material is sufficiently improved, and the first coulomb efficiency and the reversible capacity of the electrode are improved. The first coulombic efficiency of the composite electrode material under the multiplying power of 0.1C is 75-85%, and the first reversible capacity is 850-950 mAh/g.
And secondly, the zinc oxide component with electrochemical activity is uniformly filled into the pores in the nickel nanosheet array, the pores are uniformly compounded, and the nickel nanosheet array serves as a three-dimensional buffer network and a conductive network in the zinc oxide layer, so that the structural stability of the electrode is enhanced, the conductivity of the electrode is improved, and the cycle performance and the high rate performance of the zinc oxide are improved. The reversible capacity retention rate of the composite electrode material after 100 cycles at 0.1C rate is 80-95%; the first capacities at 0.5, 1 and 2C multiplying power are respectively 750-850, 650-750 and 500-600 mAh/g.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the examples will be briefly described below.
Fig. 1 is a schematic diagram of a preparation process of a zinc oxide composite electrode material loaded on a nickel nanosheet array in an embodiment.
Fig. 2 is a scanning electron micrograph of the zinc oxide composite electrode material loaded by the nickel nanosheet array in the example.
Detailed Description
The present invention will be further specifically described below by way of specific examples, but the present invention is not limited to the following examples.
Example (b):
(1) placing nickel foil in a mixed solution composed of nickel sulfate and potassium persulfate, wherein the concentration of nickel sulfate is 0.4 mol/L, the concentration of potassium persulfate is 0.075 mol/L, continuously stirring and heating to 25oAnd C, putting the substrate into a nickel foil substrate with the size of 1 cm multiplied by 1 cm, adding 10 mL of concentrated ammonia water to trigger a deposition reaction, taking out after 60 min, washing with deionized water and drying to obtain the nickel oxyhydroxide array.
(2) And (2) adopting a radio frequency magnetron sputtering technology, taking zinc oxide ceramic as a target material, installing the target material at a position 20 cm above the sample table, and sputtering and depositing a zinc oxide coating on the vertical hydroxyl nickel oxide array obtained in the step (1). The sputtering atmosphere is high-purity argon (99.999%), the working pressure is 8 mTorr, the sputtering power is 60W, and the sputtering time is 8 h.
(3) Adopting a reduction method, taking hydrogen-argon mixed gas containing 5 percent of hydrogen as a reduction gas,reducing the hydroxyl nickel oxide in the composite material obtained in the step (2) into metallic nickel at the reduction temperature of 400 DEG CoC, reducing for 2 h to finally prepare the nickel nanosheet array loaded zinc oxide composite electrode material, wherein the thickness of the nickel nanosheet array loaded zinc oxide composite electrode material is 2 microns, and the areal density of nickel is 0.25 mg/cm2The surface density of the zinc oxide is 0.75 mg/cm2。
The electrochemical performance of the material is tested by adopting a CR2025 button cell, a nickel nanosheet array loaded zinc oxide composite electrode is used as a working electrode, a lithium sheet is used as a counter electrode, and 1 mol/L LiPF6The DEC + EC (volume ratio DEC: EC = 1: 1) solution of (A) was used as an electrolyte, and Celgard2400 polypropylene membrane was used as a separator. The cell assembly process was completed in a glove box with water and oxygen concentrations below 1 ppm. And standing the battery for 12 h after the battery is assembled, and performing constant-current charge and discharge on the battery by adopting a constant-current charge and discharge method at different multiplying powers within a voltage range of 0.02-3.0V, and testing reversible capacity, first coulombic efficiency, cycle performance and high multiplying power performance.
According to the nickel nanosheet array loaded zinc oxide composite electrode material, an obvious composite effect exists between the nickel nanosheet array and a zinc oxide active material, and the electrochemical performance of the nickel nanosheet array loaded zinc oxide composite electrode material is obviously enhanced. Compared with the conventional pure zinc oxide cathode material prepared by depositing on a flat nickel foil by the same magnetron sputtering process, the material has the following advantages:
1. the first coulomb efficiency and reversible capacity are obviously improved. In the composite electrode, the nano nickel can perform reversible conversion reaction with lithium oxide generated after zinc oxide is discharged for the first time (Ni + Li)2O ↔ NiO + 2Li) to allow more electrode materials to participate in the electrochemical reaction, thereby improving the first coulombic efficiency and reversible capacity. The first coulombic efficiency and the first reversible capacity of the nickel nanosheet array loaded zinc oxide composite electrode of the embodiment of the invention are compared with the first reversible capacity of a conventional pure zinc oxide electrode under the multiplying power of 0.1C, which is shown in Table 1.
TABLE 1
Figure 273519DEST_PATH_IMAGE001
2. The cycle performance is obviously improved. The combination of the nickel nanosheet array and the zinc oxide improves the structural strength of the electrode, and a three-dimensional buffer network is formed in the zinc oxide, so that the stability of the electrode in the repeated circulation process is ensured, and the circulation performance of the electrode is improved. The comparison of the reversible capacity retention rate of the zinc oxide composite electrode material loaded on the nickel nanosheet array in the embodiment of the invention and the conventional pure zinc oxide electrode after 100 cycles at 0.1 ℃ is also shown in table 1.
3. The high rate performance is obviously enhanced. The nickel nanosheet array forms a three-dimensional conductive network in the zinc oxide, so that the overall conductivity of the electrode is improved, and the polarization of the electrode is reduced, thereby improving the high-rate performance of the electrode. Table 2 compares the first reversible capacities at 0.5, 1, and 2C rates of the nickel nanosheet array loaded zinc oxide composite electrode of the example of the present invention and a conventional pure zinc oxide electrode.
TABLE 2
Figure 855679DEST_PATH_IMAGE002

Claims (4)

1. A preparation method of a nickel nanosheet array loaded zinc oxide composite electrode material is characterized by comprising the following steps:
(1) vertically growing a hydroxyl nickel oxide nanosheet array on a nickel foil substrate by adopting a chemical water bath deposition method;
(2) further depositing zinc oxide on the nickel oxyhydroxide array obtained in the step (1) by adopting a radio frequency magnetron sputtering method to obtain a nickel oxyhydroxide nanosheet array loaded zinc oxide composite material;
(3) and (3) reducing the hydroxyl nickel oxide in the composite material obtained in the step (2) into metallic nickel by using hydrogen-argon mixed gas by adopting a reduction method, and finally obtaining the nickel nanosheet array loaded zinc oxide composite electrode material.
2. The method for preparing the nickel nanosheet array-supported zinc oxide composite electrode material of claim 1, wherein in step (1), the reaction solutionIs a mixed solution composed of nickel sulfate and potassium persulfate, wherein the concentration of the nickel sulfate is 0.2-0.6 mol/L, the concentration of the potassium persulfate is 0.05-0.1 mol/L, 5-15 mL of concentrated ammonia water is added to trigger a deposition reaction, and the reaction temperature is 10-40oC, the reaction time is 0.5-3 h; in the step (2), the target is zinc oxide ceramic, the radio frequency power is 50-100W, and the sputtering time is 2-12 h; in the step (3), the reducing atmosphere is hydrogen-argon mixed gas, and the reducing temperature is 300-500 DEG C oAnd C, the reaction time is 1-3 h.
3. A nickel nanosheet array loaded zinc oxide composite electrode material prepared according to the method of claim 2.
4. The application of the nickel nanosheet array-supported zinc oxide composite electrode material of claim 3 as an electrode material for a lithium ion battery.
CN201811087345.XA 2018-09-18 2018-09-18 Nickel nanosheet array loaded zinc oxide composite electrode and preparation method thereof Active CN109301198B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811087345.XA CN109301198B (en) 2018-09-18 2018-09-18 Nickel nanosheet array loaded zinc oxide composite electrode and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811087345.XA CN109301198B (en) 2018-09-18 2018-09-18 Nickel nanosheet array loaded zinc oxide composite electrode and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109301198A CN109301198A (en) 2019-02-01
CN109301198B true CN109301198B (en) 2021-02-26

Family

ID=65163495

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811087345.XA Active CN109301198B (en) 2018-09-18 2018-09-18 Nickel nanosheet array loaded zinc oxide composite electrode and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109301198B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109817879B (en) * 2019-03-19 2020-08-14 北京航空航天大学 Zinc metal composite electrode with array structure and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173495A (en) * 2008-01-25 2009-08-06 Univ Of Miyazaki Nickel hydroxide nanosheet and its manufacturing method
CN101774653A (en) * 2010-02-05 2010-07-14 北京化工大学 Alpha-nickel hydroxide nano/micro structure material and preparation method thereof
CN103985836A (en) * 2014-05-27 2014-08-13 哈尔滨工业大学 Method for preparing germanium cathode material on nickel nanoneedle conical array
CN105033241A (en) * 2015-06-04 2015-11-11 北京化工大学 Ultrathin metallic nickel nanosheet, manufacturing method thereof and application of nanosheets as electrode materials
CN105140464A (en) * 2015-08-10 2015-12-09 复旦大学 Nano composite material of carbon-coated nickel oxide nanosheet-loaded graphene and preparation method of nano composite material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173495A (en) * 2008-01-25 2009-08-06 Univ Of Miyazaki Nickel hydroxide nanosheet and its manufacturing method
CN101774653A (en) * 2010-02-05 2010-07-14 北京化工大学 Alpha-nickel hydroxide nano/micro structure material and preparation method thereof
CN103985836A (en) * 2014-05-27 2014-08-13 哈尔滨工业大学 Method for preparing germanium cathode material on nickel nanoneedle conical array
CN105033241A (en) * 2015-06-04 2015-11-11 北京化工大学 Ultrathin metallic nickel nanosheet, manufacturing method thereof and application of nanosheets as electrode materials
CN105140464A (en) * 2015-08-10 2015-12-09 复旦大学 Nano composite material of carbon-coated nickel oxide nanosheet-loaded graphene and preparation method of nano composite material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Fe2O3 Nanoneedles on Ultrafine Nickel Nanotube Arrays as efficient anode for high-performance asymmetric supercapacitors;Yang Li等;《Advanced Funct.Mater》;20170301;第2017卷(第27期);第160728（1-10）页 *
ZnO nanoparticles anchored on nickel foam with graphene as morphology-controlling agent for high-performance lithium-ion battery anodes;Jian Zheng 等;《J APPL Electrochem》;20170623;第969-978页 *
镍基纳米材料/复合物的制备及其电化学性能的研究;朱建慧;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20140915(第9期);第B020-5页 *

Also Published As

Publication number Publication date
CN109301198A (en) 2019-02-01

Similar Documents

Publication Publication Date Title
CN109004199B (en) Preparation method of biomass hard carbon material for negative electrode of sodium-ion battery
KR101758967B1 (en) Battery
CN106229498B (en) Cathode material suitable for water-based metal ion battery and preparation method thereof
CN102169996B (en) Micro-sphere compound anode material with core-shell structure and preparation method thereof
CN108598394B (en) Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof
CN110808179B (en) Nitrogen-oxygen co-doped biomass hard carbon material and preparation method and application thereof
CN112850796B (en) S/Fe for preparing lithium-sulfur battery positive electrode material 3 O 4 Method for producing MXene
CN112133896A (en) High-capacity graphite-silicon oxide composite material and preparation method and application thereof
CN115072703A (en) Composite negative electrode material and preparation method and application thereof
CN109301198B (en) Nickel nanosheet array loaded zinc oxide composite electrode and preparation method thereof
CN108987673B (en) Lithium negative electrode containing conductive protection film and preparation method and application thereof
CN114843459B (en) Antimony pentasulfide-based material and preparation method and application thereof
CN116470003A (en) Pre-lithiated negative electrode piece and lithium ion battery
CN115974033A (en) Nitrogen-doped mesoporous carbon-coated iron sodium phosphate pyrophosphate composite material and preparation method thereof
CN115566170A (en) Preparation method of high-energy-density quick-charging lithium ion battery cathode material
CN115275168A (en) High-rate lithium ion battery negative electrode material and preparation method thereof
CN103427119A (en) Battery with a battery cell
CN112510196A (en) Preparation method of manganese-based metal oxide positive electrode
CN111261857B (en) FePS for sodium ion battery3/NC composite negative electrode material, preparation method thereof and sodium ion battery
CN112209430B (en) Tin dioxide/niobium doped carbon composite material for lithium ion battery and preparation method and application thereof
CN114583137B (en) Method for modifying carbon surface by sulfur doped phosphorus and application thereof
CN113130903B (en) Aluminum oxide coated iron cyanamide material prepared by sol-gel method and preparation method and application thereof
CN114171713A (en) Modified graphite cathode and preparation method thereof
CN117199297A (en) Carbon nitride and vanadium carbide co-coated manganese oxide composite material and preparation method and application thereof
WO2022099595A1 (en) Composite silicon monoxide thin film, preparation method therefor and use thereof

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