CN108832100B - A kind of preparation method of carbon-coated zinc ferrite/graphene composite negative electrode material - Google Patents
A kind of preparation method of carbon-coated zinc ferrite/graphene composite negative electrode material Download PDFInfo
- Publication number
- CN108832100B CN108832100B CN201810618507.1A CN201810618507A CN108832100B CN 108832100 B CN108832100 B CN 108832100B CN 201810618507 A CN201810618507 A CN 201810618507A CN 108832100 B CN108832100 B CN 108832100B
- Authority
- CN
- China
- Prior art keywords
- carbon
- zinc ferrite
- zinc
- negative electrode
- hours
- 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
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 87
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229920001448 anionic polyelectrolyte Polymers 0.000 claims abstract description 12
- 150000003751 zinc Chemical class 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 239000006185 dispersion Substances 0.000 claims description 70
- 239000000843 powder Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 229930091371 Fructose Natural products 0.000 claims description 5
- 239000005715 Fructose Substances 0.000 claims description 5
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 5
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 5
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229920000867 polyelectrolyte Polymers 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000011787 zinc oxide Substances 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- -1 polyethylene phosphoric acid Polymers 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 2
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
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
-
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Hard Magnetic Materials (AREA)
Abstract
本发明涉及一种碳包覆铁酸锌/石墨烯复合负极材料的制备方法。以糖为原料通过水热法制备碳颗粒模板；以碳颗粒为模板，加入锌盐和铁盐，以碱为沉淀剂制备铁酸锌前驱体，在空气气氛中通过前驱体热解法获得铁酸锌纳米颗粒；分两步分别加入阴离子型聚电解质和氧化石墨烯，在氮气气氛中烧结得到目标碳包覆铁酸锌/石墨烯复合负极材料。本发明操作简单，易于批量生产，所用水或乙醇溶剂对环境友好。通过这种方法得到的复合负极材料中铁酸锌尺寸在20纳米左右，薄的2纳米的碳层均匀包覆在铁酸锌纳米颗粒外层，并且碳层与铁酸锌有强的共价键作用，石墨烯与碳层形成双重碳包覆结构，使复合负极材料形成三维导电网络，该复合材料具有优异的倍率性能和循环性能。
The invention relates to a preparation method of a carbon-coated zinc ferrite/graphene composite negative electrode material. Using sugar as raw material to prepare carbon particle template by hydrothermal method; using carbon particle as template, adding zinc salt and iron salt, using alkali as precipitant to prepare zinc ferrite precursor, and obtaining iron by precursor pyrolysis in air atmosphere Zinc oxide nanoparticles; adding anionic polyelectrolyte and graphene oxide in two steps, and sintering in nitrogen atmosphere to obtain the target carbon-coated zinc ferrite/graphene composite negative electrode material. The invention is simple to operate, easy to produce in batches, and the water or ethanol solvent used is environmentally friendly. The size of zinc ferrite in the composite negative electrode material obtained by this method is about 20 nanometers, a thin 2 nanometer carbon layer is uniformly coated on the outer layer of zinc ferrite nanoparticles, and the carbon layer has a strong covalent bond with zinc ferrite. The graphene and the carbon layer form a double carbon coating structure, so that the composite negative electrode material forms a three-dimensional conductive network, and the composite material has excellent rate performance and cycle performance.
Description
Technical Field
The invention belongs to the technical field of electrode materials and application thereof, and particularly relates to a preparation method of a carbon-coated zinc ferrite/graphene composite negative electrode material.
Background
Lithium ion batteries are widely used in various portable electronic products due to their advantages of high energy density, high operating voltage, long service life, environmental friendliness, and no memory effect. However, with the rapid development of electric vehicles and large-scale energy storage devices, higher requirements are placed on the capacity, energy density and rapid charging and discharging capability of lithium ion batteries. The development of high-performance electrode materials is a key factor for improving the performance of lithium ion batteries. Most of the current commercialized lithium ion battery negative electrode materials use graphite carbon materials, but lithium dendrite is easy to generate in the charging and discharging process, the hidden danger of battery explosion exists, the theoretical specific capacity is low (372 mAh/g), and the requirement of a new generation of high-capacity energy storage equipment is difficult to meet. Therefore, the search for high-capacity, long-cycle-life and high-safety cathode materials has become the focus of research on lithium ion batteries.
The transition metal oxide has a high theoretical specific capacity (500-1000 mAh/g), so that the transition metal oxide attracts wide attention. Among them, zinc ferrite has higher theoretical capacity (1000.5 mAh/g) and lower lithium-intercalation-deintercalation platform than common transition metal oxide, and has rich raw material sources, no toxicity, environmental protection and safety, thus being favored. However, zinc ferrite has the defects of poor conductivity, large volume change of the material in the charging and discharging processes and easy agglomeration, so that the cycle performance and rate capability of the material are greatly reduced.
Aiming at the problem, the performance of the zinc ferrite negative electrode material is improved mainly by nanocrystallizing the material and compounding the material with a carbon material at present. However, the current zinc ferrite-carbon composite negative electrode material has the main defects that: (1) the zinc ferrite has magnetism and is easy to agglomerate in the preparation process, so that the obtained composite material is not uniform; (2) the zinc ferrite and the carbon material have different volume expansion rates in the charging and discharging processes, so that the zinc ferrite and the carbon material are easy to separate; (3) the interface performance of zinc ferrite and carbon materials is poor.
Disclosure of Invention
Aiming at the defects of a pure-phase zinc ferrite negative electrode material, firstly preparing nano-scale zinc ferrite, taking an anionic polyelectrolyte of a polyacid as a carbon source to enable the zinc ferrite and carbon to generate strong covalent bond action, and then introducing graphene to form a three-dimensional conductive network structure, so that the carbon-coated zinc ferrite/graphene composite negative electrode material is prepared, and the problems of poor conductivity, poor cycle performance and poor rate capability of the electrode material are solved.
The invention provides a preparation method of a carbon-coated zinc ferrite/graphene composite negative electrode material, which comprises the following specific steps:
(1) dissolving sugar in deionized water to obtain a sugar solution with the concentration of 0.2-2 mol/L, then placing the sugar solution in a hydrothermal kettle, heating at 140-200 ℃ for 2-10 hours, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc salt and iron salt in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion solution, and magnetically stirring the solution for 0.1 to 10 hours to obtain a first mixed dispersion solution; slowly dropwise adding an alkaline ethanol solution into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then placing the obtained powder in a tube furnace, calcining for 0.5-5 hours at 800 ℃ in an air atmosphere of 200-: the molar ratio of zinc to iron in the zinc salt and the iron salt is 1.5:2, and the molar ratio of the zinc salt to alkali is 1.5: 9;
(3) ultrasonically dispersing the zinc ferrite powder obtained in the step (2) in deionized water, adding anionic polyelectrolyte, and magnetically stirring for 0.1-10 hours to obtain a mixed dispersion of the zinc ferrite and the anionic polyelectrolyte; then ultrasonically dispersing graphite oxide powder into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and anionic polyelectrolyte, and continuously magnetically stirring for 0.1-10 hours to obtain a second mixed dispersion; placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 0.5-5 hours at 800 ℃ in a nitrogen atmosphere to obtain a carbon-coated zinc ferrite/graphene composite negative electrode material; the mass ratio of the zinc ferrite to the anionic polyelectrolyte is 1: (0.1-2); the mass ratio of the zinc ferrite to the graphite oxide is 1: (0.1-2).
In the present invention, the sugar in step (1) is any one of glucose, fructose and sucrose.
In the invention, the zinc salt in the step (2) is any one of zinc chloride, zinc nitrate, zinc sulfate, zinc acetate or corresponding crystalline hydrate.
In the invention, the ferric salt in the step (2) is any one of ferric chloride, ferric nitrate, ferric sulfate, ferric acetate or corresponding crystalline hydrate.
In the present invention, the ratio of the carbon particles to the zinc salt in the step (2) is (50-500 mg): 1 millimole.
In the invention, the alkali in the step (2) is any one of sodium hydroxide, potassium hydroxide or ammonia water.
In the invention, the anionic polyelectrolyte in the step (3) is a polyacid polyelectrolyte, specifically any one of polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or polyvinyl phosphoric acid.
The invention has the advantages that: firstly, zinc ferrite nano-particles with uniform size are obtained by means of a carbon particle template, the size of the zinc ferrite nano-particles is about 20 nanometers, secondly, the high-affinity polyacid type anion polyelectrolyte is used as a carbon source, so that the zinc ferrite and the carbon source have a strong effect, the agglomeration of the zinc ferrite in the carbon coating process is reduced, and a uniform carbon-coated zinc ferrite composite material is obtained, thirdly, graphene is introduced into the carbon-coated zinc ferrite composite material to form a three-dimensional conductive network structure, so that the problem of poor conductivity of an electrode material is solved, moreover, after high-temperature carbonization, the zinc ferrite and carbon have a strong covalent bond effect, so that the composite material is not separated in the charging and discharging process, and the obtained carbon-coated zinc ferrite/graphene composite negative electrode material has excellent cycle performance (the specific discharge capacity is up to 942 mAh/g after 500 times of cyclic charging and discharging under the current density of 0.2A/g) and rate performance (the specific discharge capacity under the current density of 5A/g is 0.1 67.8% of the specific discharge capacity at A/g current density). The scheme is simple to operate and easy for batch production, solves the key problems of poor cycle life and rate performance of zinc ferrite, and provides an effective way for realizing the application of the zinc ferrite material in the cathode of the lithium ion battery.
Drawings
Fig. 1 is an X-ray diffraction spectrum of a carbon-coated zinc ferrite/graphene composite negative electrode material.
FIG. 2 is a field emission scanning electron micrograph of zinc ferrite.
FIG. 3 is a transmission electron micrograph of carbon-coated zinc ferrite.
FIG. 4 is a field emission scanning electron microscope photograph of the carbon-coated zinc ferrite/graphene composite negative electrode material.
Fig. 5 is a rate performance diagram of the carbon-coated zinc ferrite/graphene composite negative electrode material.
FIG. 6 is a cycle performance diagram of the carbon-coated zinc ferrite/graphene composite negative electrode material at 0.2A/g.
Detailed Description
The following further describes a specific embodiment of a method for preparing a carbon-coated zinc ferrite/graphene composite anode material according to the present invention with reference to the drawings, and examples are provided to facilitate understanding of the present invention, but the present invention is by no means limited thereto, and the present invention is not limited to the following embodiments. Other insubstantial changes from the above disclosure are intended to be covered by the present invention.
Example 1
(1) Dissolving glucose in deionized water to obtain a glucose solution with the concentration of 0.5 mol/L, then placing the glucose solution in a hydrothermal kettle, heating for 8 hours at 180 ℃, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder (150 mg) obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc chloride (1.5 mmol) and ferric chloride hexahydrate (2 mmol) in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion solution, and magnetically stirring for 5 hours to obtain a first mixed dispersion solution; slowly dropwise adding an ethanol solution of ammonia water (9 millimoles) into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then putting the obtained powder into a tubular furnace, calcining for 2 hours at the air atmosphere of 500 ℃ to obtain zinc ferrite powder; (3) ultrasonically dispersing the zinc ferrite powder (100 mg) obtained in the step (2) in deionized water, adding polyacrylic acid (50 mg), and magnetically stirring for 5 hours to obtain a mixed dispersion liquid of the zinc ferrite and the polyacrylic acid; then, ultrasonically dispersing graphite oxide powder (20 mg) into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and polyacrylic acid, and continuing to magnetically stir for 5 hours to obtain a second mixed dispersion; and placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain the carbon-coated zinc ferrite/graphene composite negative electrode material.
The zinc ferrite in the obtained carbon-coated zinc ferrite/graphene composite negative electrode material can be seen as a spinel structure through X-ray diffraction (figure 1). The field emission scanning electron micrograph shows that the preparation method successfully obtains uniform zinc ferrite nano particles with the diameter of about 20 nanometers (figure 2). FIG. 3 shows that 2 nm carbon layer is uniformly coated on the surface of zinc ferrite. Fig. 4 shows that carbon-coated zinc ferrite nanoparticles are coated with a thin layer of graphene. From the rate performance graph, it can be known that the specific discharge capacity of the carbon-coated zinc ferrite/graphene composite negative electrode material under the current density of 5A/g is 67.8% of the specific discharge capacity under the current density of 0.1A/g (fig. 5). FIG. 6 shows a cycle performance diagram, in which the specific discharge capacity of the carbon-coated zinc ferrite/graphene composite negative electrode material reaches 942 mAh/g after being charged and discharged for 500 times under 0.2A/g, which is 99.2% of the specific discharge capacity of the second time.
Example 2
(1) Dissolving fructose in deionized water to obtain a fructose solution with the concentration of 1 mol/L, then placing the fructose solution in a hydrothermal kettle, heating for 8 hours at 160 ℃, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder (200 mg) obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc nitrate hexahydrate (1.5 mmol) and ferric nitrate nonahydrate (2 mmol) in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion, and magnetically stirring for 0.1 hour to obtain a first mixed dispersion; slowly dropwise adding an ethanol solution of sodium hydroxide (9 millimoles) into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then putting the obtained powder into a tubular furnace, calcining for 0.5 hour at 800 ℃ in air atmosphere to obtain zinc ferrite powder;
(3) ultrasonically dispersing the zinc ferrite powder (100 mg) obtained in the step (2) in deionized water, adding polymethacrylic acid (150 mg), and magnetically stirring for 10 hours to obtain a mixed dispersion of the zinc ferrite and the polymethacrylic acid; then, ultrasonically dispersing graphite oxide powder (10 mg) into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and polymethacrylic acid, and continuing to magnetically stir for 0.1 hour to obtain a second mixed dispersion; and placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 0.5 hour at 500 ℃ in a nitrogen atmosphere to obtain the carbon-coated zinc ferrite/graphene composite negative electrode material.
Example 3
(1) Dissolving sucrose in deionized water to obtain a sucrose solution with the concentration of 0.2 mol/L, then placing the sucrose solution in a hydrothermal kettle, heating for 2 hours at 180 ℃, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder (250 mg) obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc sulfate heptahydrate (1.5 mmol) and ferric sulfate (1 mmol) in ethanol, dropwise adding into the carbon particle-ethanol dispersion, and magnetically stirring for 10 hours to obtain a first mixed dispersion; slowly dropwise adding an ethanol solution of ammonia water (9 millimoles) into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then placing the obtained powder in a tubular furnace, calcining for 5 hours at the temperature of 400 ℃ in air atmosphere to obtain zinc ferrite powder;
(3) ultrasonically dispersing the zinc ferrite powder (100 mg) obtained in the step (2) in deionized water, adding polystyrene sulfonic acid (10 mg), and magnetically stirring for 0.1 hour to obtain a mixed dispersion liquid of the zinc ferrite and the polystyrene sulfonic acid; then, ultrasonically dispersing graphite oxide powder (200 mg) into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and polystyrene sulfonic acid, and continuing to magnetically stir for 5 hours to obtain a second mixed dispersion; and placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 5 hours at 800 ℃ in a nitrogen atmosphere to obtain the carbon-coated zinc ferrite/graphene composite negative electrode material.
Example 4
(1) Dissolving glucose in deionized water to obtain a glucose solution with the concentration of 2 mol/L, then placing the glucose solution in a hydrothermal kettle, heating for 8 hours at 140 ℃, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder (75 mg) obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc chloride (1.5 mmol) and ferric chloride hexahydrate (2 mmol) in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion solution, and magnetically stirring for 8 hours to obtain a first mixed dispersion solution; slowly dropwise adding an ethanol solution of potassium hydroxide (9 millimoles) into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then putting the obtained powder into a tubular furnace, calcining for 3 hours at the air atmosphere of 200 ℃ to obtain zinc ferrite powder;
(3) ultrasonically dispersing the zinc ferrite powder (100 mg) obtained in the step (2) in deionized water, adding polyacrylic acid (50 mg), and magnetically stirring for 5 hours to obtain a mixed dispersion liquid of the zinc ferrite and the polyacrylic acid; then, ultrasonically dispersing graphite oxide powder (100 mg) into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and polyacrylic acid, and continuing to magnetically stir for 10 hours to obtain a second mixed dispersion; and placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 3 hours at 200 ℃ in a nitrogen atmosphere to obtain the carbon-coated zinc ferrite/graphene composite negative electrode material.
Example 5
(1) Dissolving glucose in deionized water to obtain a glucose solution with the concentration of 0.5 mol/L, then placing the glucose solution in a hydrothermal kettle, heating for 10 hours at 200 ℃, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder (750 mg) obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc chloride (1.5 mmol) and ferric chloride hexahydrate (2 mmol) in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion solution, and magnetically stirring for 5 hours to obtain a first mixed dispersion solution; slowly dropwise adding an ethanol solution of sodium hydroxide (9 millimoles) into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then placing the obtained powder in a tubular furnace, calcining for 1 hour at 600 ℃ in air atmosphere to obtain zinc ferrite powder;
(3) ultrasonically dispersing the zinc ferrite powder (100 mg) obtained in the step (2) in deionized water, adding polyethylene phosphoric acid (50 mg), and magnetically stirring for 5 hours to obtain a mixed dispersion of the zinc ferrite and the polyethylene phosphoric acid; then, ultrasonically dispersing graphite oxide powder (50 mg) into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and polyethylene phosphate, and continuing to magnetically stir for 8 hours to obtain a second mixed dispersion; and placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 4 hours at the temperature of 400 ℃ in a nitrogen atmosphere to obtain the carbon-coated zinc ferrite/graphene composite negative electrode material.
Claims (5)
1. A preparation method of a carbon-coated zinc ferrite/graphene composite negative electrode material is characterized by comprising the following specific steps:
(1) dissolving sugar in deionized water to obtain a sugar solution with the concentration of 0.2-2 mol/L, then placing the sugar solution in a hydrothermal kettle, heating at 140-200 ℃ for 2-10 hours, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc salt and iron salt in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion solution, and magnetically stirring the solution for 0.1 to 10 hours to obtain a first mixed dispersion solution; slowly dropwise adding an alkaline ethanol solution into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then placing the obtained powder in a tube furnace, calcining for 0.5-5 hours at 800 ℃ in an air atmosphere of 200-: the molar ratio of zinc to iron in the zinc salt and the iron salt is 1.5:2, and the molar ratio of the zinc salt to alkali is 1.5: 9; the ratio of carbon particles to zinc salt is (50-500 mg): 1 millimole;
(3) ultrasonically dispersing the zinc ferrite powder obtained in the step (2) in deionized water, adding anionic polyelectrolyte, and magnetically stirring for 0.1-10 hours to obtain a mixed dispersion of the zinc ferrite and the anionic polyelectrolyte; then ultrasonically dispersing graphite oxide powder into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and anionic polyelectrolyte, and continuously magnetically stirring for 0.1-10 hours to obtain a second mixed dispersion; placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 0.5-5 hours at 800 ℃ in a nitrogen atmosphere to obtain a carbon-coated zinc ferrite/graphene composite negative electrode material; the mass ratio of the zinc ferrite to the anionic polyelectrolyte is 1: (0.1-2); the mass ratio of the zinc ferrite to the graphite oxide is 1: (0.1-2); the anionic polyelectrolyte is a polyacid polyelectrolyte, specifically any one of polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or polyvinyl phosphoric acid.
2. The method for preparing the carbon-coated zinc ferrite/graphene composite anode material according to claim 1, wherein the sugar in the step (1) is any one of glucose, fructose and sucrose.
3. The preparation method of the carbon-coated zinc ferrite/graphene composite negative electrode material according to claim 1, wherein the zinc salt in the step (2) is any one of zinc chloride, zinc nitrate, zinc sulfate, zinc acetate or corresponding crystalline hydrate.
4. The preparation method of the carbon-coated zinc ferrite/graphene composite anode material according to claim 1, wherein the iron salt in the step (2) is any one of ferric chloride, ferric nitrate, ferric sulfate, ferric acetate or corresponding crystalline hydrate.
5. The method for preparing the carbon-coated zinc ferrite/graphene composite anode material according to claim 1, wherein the alkali in the step (2) is any one of sodium hydroxide, potassium hydroxide or ammonia water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810618507.1A CN108832100B (en) | 2018-06-15 | 2018-06-15 | A kind of preparation method of carbon-coated zinc ferrite/graphene composite negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810618507.1A CN108832100B (en) | 2018-06-15 | 2018-06-15 | A kind of preparation method of carbon-coated zinc ferrite/graphene composite negative electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108832100A CN108832100A (en) | 2018-11-16 |
| CN108832100B true CN108832100B (en) | 2021-02-26 |
Family
ID=64142427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810618507.1A Active CN108832100B (en) | 2018-06-15 | 2018-06-15 | A kind of preparation method of carbon-coated zinc ferrite/graphene composite negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108832100B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016337B (en) * | 2019-01-22 | 2021-10-26 | 复旦大学 | Preparation method of metal hydroxide quantum dots |
| CN111834616B (en) * | 2019-04-23 | 2021-11-16 | 四川佰思格新能源有限公司 | Composite negative electrode material, preparation method and lithium ion battery |
| CN111725510B (en) * | 2020-06-28 | 2021-11-16 | 深圳市鹏锦生混凝土有限公司 | Lithium battery negative electrode material and preparation process thereof |
| CN112175333B (en) * | 2020-09-24 | 2021-11-23 | 河南黄河旋风股份有限公司 | Preparation method and application of nanocomposite PMMA @ Fe-N-C |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032375A (en) * | 2015-06-24 | 2015-11-11 | 南京理工大学 | Preparation method of magnetic graphite-based heavy metal adsorbing material |
| CN105161246A (en) * | 2015-08-21 | 2015-12-16 | 盐城工学院 | Nickel-zinc ferrite/polyacrylic acid nano-composite material and preparation method thereof |
| CN105355877A (en) * | 2015-11-06 | 2016-02-24 | 盐城工学院 | Graphene-metal oxide composite negative electrode material and preparation method therefor |
| CN107871850A (en) * | 2016-09-28 | 2018-04-03 | 华为技术有限公司 | A kind of silicon/graphene composite film electrode and preparation method thereof and lithium ion battery |
-
2018
- 2018-06-15 CN CN201810618507.1A patent/CN108832100B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032375A (en) * | 2015-06-24 | 2015-11-11 | 南京理工大学 | Preparation method of magnetic graphite-based heavy metal adsorbing material |
| CN105161246A (en) * | 2015-08-21 | 2015-12-16 | 盐城工学院 | Nickel-zinc ferrite/polyacrylic acid nano-composite material and preparation method thereof |
| CN105355877A (en) * | 2015-11-06 | 2016-02-24 | 盐城工学院 | Graphene-metal oxide composite negative electrode material and preparation method therefor |
| CN107871850A (en) * | 2016-09-28 | 2018-04-03 | 华为技术有限公司 | A kind of silicon/graphene composite film electrode and preparation method thereof and lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| Graphene anchored with ZnFe2O4 nanoparticles as a high-capacity anode material for lithium-ion batteries;Hui Xia，et al;《Solid State Sciences》;20121212;第67-71页 * |
| ZnFe2O4-nanocrystal-assembled microcages as an anode material for high performance lithium-ion batteries;Chundong Wang，et al;《Materials Today Energy》;20170124;第1-8页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108832100A (en) | 2018-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108899504B (en) | A kind of antimony-carbon nanotube-carbon composite material, preparation method and application | |
| CN108832100B (en) | A kind of preparation method of carbon-coated zinc ferrite/graphene composite negative electrode material | |
| CN107069023B (en) | A kind of preparation method of hollow structure lithium ion battery electrode material | |
| CN104755429B (en) | The preparation method of ferric oxide nano particles | |
| CN108695495B (en) | Reduced graphene oxide modified antimony trisulfide battery anode material | |
| CN104966824A (en) | A kind of nitrogen-doped porous carbon sphere-cobalt oxide nanocomposite negative electrode material based on chitosan and its derivatives and its preparation method | |
| CN107732239A (en) | A kind of preparation method of lithium/sodium ion low temperature battery ferrous sulfide/carbon coating negative material | |
| CN109659544B (en) | Preparation method of graphene-coated bimetallic sulfide lithium/sodium ion battery negative electrode material | |
| CN108172770B (en) | Carbon-coated NiP with monodisperse structural featuresxNano composite electrode material and preparation method thereof | |
| KR20120113995A (en) | Nano composite materials, method for preparing the same, and energy storage device comprising the same | |
| CN106058181A (en) | Preparation method of graphene-supported carbon-coated silicone nanoparticle composite electrode material | |
| CN102185147B (en) | Nano iron phosphate hollow sphere/graphene composite material and preparation method thereof | |
| CN107611388A (en) | A kind of shell has the preparation method of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure | |
| CN106981643B (en) | A method for preparing double-layer carbon-coated manganese oxide electrode material by carbonization of biogel | |
| CN108598410A (en) | A kind of preparation method of lithium-sulfur cell sandwich material | |
| CN108987729B (en) | A kind of lithium-sulfur battery cathode material and preparation method thereof, and lithium-sulfur battery | |
| CN110707301A (en) | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof | |
| CN105870447A (en) | Preparation method of nitrogen-doped rutile TiO2/C negative electrode material for sodium ion battery | |
| CN110581264B (en) | High-performance nickel-zinc battery negative electrode active material and preparation method thereof | |
| CN113921762B (en) | Nano bismuth composite material and preparation method and application thereof | |
| CN110444740A (en) | A method of the small scale nanometer composite material of synthesizing graphite alkene/carbon-coated LiFePO 4 for lithium ion batteries is acted on by aniline polymerization confinement | |
| CN105958037A (en) | Copper sulphide/graphene composite material for negative electrode of sodium-ion battery and preparation method | |
| CN103531789A (en) | Iron oxide-carbon nanotube ternary composite material and preparation method thereof | |
| CN105261755A (en) | Preparation method for nano-rod iron molybdate electrode material of lithium ion battery | |
| Majeed et al. | Metal–organic framework mediated nickel doped copper ferrite for superior lithium storage |
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 |