CN115036502A - Based on ZnCo 2 O 4 Method for preparing sodium ion battery cathode material by hollow carbon nanorings and application - Google Patents
Based on ZnCo 2 O 4 Method for preparing sodium ion battery cathode material by hollow carbon nanorings and application Download PDFInfo
- Publication number
- CN115036502A CN115036502A CN202210773724.4A CN202210773724A CN115036502A CN 115036502 A CN115036502 A CN 115036502A CN 202210773724 A CN202210773724 A CN 202210773724A CN 115036502 A CN115036502 A CN 115036502A
- Authority
- CN
- China
- Prior art keywords
- znco
- hollow carbon
- ion battery
- sodium ion
- preparing
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 80
- 239000002063 nanoring Substances 0.000 title claims abstract description 73
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 45
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000010406 cathode material Substances 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 239000007773 negative electrode material Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000011889 copper foil Substances 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 239000002086 nanomaterial Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 239000006258 conductive agent Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 9
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- -1 Co (Ac) 2 ·4H 2 O Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 6
- 239000000969 carrier Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 230000005012 migration Effects 0.000 abstract 1
- 238000013508 migration Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001579016 Nanoa Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 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
- H01M4/48—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Based on ZnCo 2 O 4 A method for preparing a sodium ion battery cathode material by using hollow carbon nano rings and application thereof. Firstly, preparing a hollow carbon nano-ring as a carrier and uniformly coating the surface of the hollow carbon nano-ringLoaded ZnCo 2 O 4 ZnCo nanoparticles 2 O 4 Hollow carbon nanoring composite material; secondly, ZnCo is mixed 2 O 4 The hollow carbon nano material, the conductive agent and the binder are mixed and then water is used as a solvent to prepare the negative electrode material of the sodium-ion battery. And finally, loading the negative electrode material on the copper foil to assemble the sodium-ion battery. The cathode material can overcome the problems of large volume expansion and poor intrinsic conductivity of metal oxide in the sodium storage process; the excellent mechanical strength, conductivity and chemical stability of the hollow carbon nano-ring are beneficial to improving the electrochemical cycle stability of the composite material, and in addition, the large specific surface area and the hollow structure are beneficial to the permeation and migration of electrolyte. The unique hollow nano-ring structure can promote the diffusion of sodium ions and prevent ZnCo 2 O 4 Agglomeration of nanoparticles to ZnCo 2 O 4 The hollow carbon nanoring composite material exhibits excellent sodium storage performance.
Description
Technical Field
The invention belongs to the field of nano material preparation and novel battery energy storage, and relates to a ZnCo-based battery 2 O 4 A method for preparing a sodium ion battery cathode material by using hollow carbon nano rings and application thereof.
Background
With the rapid development of portable electronic devices and electric vehicles, various energy storage devices have been developed. Among them, lithium ion batteries are widely used due to their excellent performance, and play an important role. However, lithium resources are very limited and cannot meet the expanding demand of energy storage field. Meanwhile, the sodium ion battery is expected to replace a lithium ion battery in the future due to rich sodium resources and low cost, and becomes a novel energy storage device capable of being utilized on a large scale. However, the electrochemical performance of the sodium ion battery is obviously different from that of the lithium ion battery. In order to obtain a sodium ion battery with higher energy density and longer cycle life, the key problem to be solved is material innovation; for example, a high-specific-capacity and high-potential cathode material is greatly developed, and development of a high-specific-capacity composite cathode material faces a great challenge.
The transition metal oxide has the characteristics of low cost, environmental friendliness, large theoretical specific capacity and the like, and is a promising sodium ionA battery negative electrode material. Wherein, Co 3 O 4 The electrode material is a classical electrode material due to higher theoretical specific capacity. However, due to large volume change, low sodium ion diffusion kinetics, large toxicity, high cost during charging and discharging, Co has a large specific surface area 3 O 4 The use in sodium ion batteries is severely hampered. Partial substitution of Co with less costly and environmentally friendly substitute elements (e.g., zinc, copper, nickel, magnesium, etc.) 3 O 4 The element Co in the composite material is coupled with two metal species, so that the conductivity is improved, and rich oxidation-reduction reaction is provided for binary transition metal oxide. Introduction of zinc ions enables Co to be incorporated due to its unchanged divalent state 3 O 4 A controllable change takes place. At the same time, ZnCo 2 O 4 The conductive metal ion has complex chemical components, and has a synergistic effect between two different metal ions, thereby showing good conductivity and electrochemical activity.
So far, various ZnCo with different nanostructures 2 O 4 Materials, including nanoparticles, nanowires, nanofibers, porous core-shell structures, and porous hollow spheres, have been widely studied as electrode materials for energy storage. Despite the great advances made, there are conventional ZnCo systems 2 O 4 The problems of large volume changes and particle agglomeration in the material have not yet been effectively overcome. To solve these problems, one effective strategy is to incorporate nano-sized ZnCo 2 O 4 Anchored on a conductive carbon substrate to build a nanocomposite, which will have a good synergistic effect.
Nanocarbon materials (graphene and carbon nanotubes) have been widely used as battery energy storage materials, but the graphene layer stacking and the mutual winding between the carbon nanotubes caused by pi-pi action seriously affect the full play of the electrochemical performance of the nanocarbon materials. The hollow carbon nanoring is used as a unique carbon nanomaterial, can adapt to severe volume expansion due to excellent mechanical strength, and can inhibit ZnCo loaded on the surface of the carbon nanoring 2 O 4 Agglomeration is carried out in the continuous charge-discharge cycle process, and the conductivity of the material is improved. In addition, the hollow carbon nanorings are porous due to the annular wall andthe cavity structure is beneficial to forming a continuous channel and greatly improves the transmission rate of electrolyte ions.
Preparation of ZnCo in general 2 O 4 Composites involve multiple reactions and are therefore often complex and time consuming and laborious to perform. From the practical applicability point of view, a more efficient and environment-friendly preparation method is developed to synthesize ZnCo with a specific structure and excellent electrochemical performance 2 O 4 Composite electrode materials still face significant challenges.
Disclosure of Invention
Aiming at the problems, the invention synthesizes ZnCo in a simple hydrothermal mode 2 O 4 Hollow carbon nanoring composite material. ZnCo 2 O 4 The hollow carbon nano-ring composite material is prepared by mixing ZnCo 2 O 4 The nano particles are uniformly loaded on the surface of the hollow carbon nano ring. ZnCo 2 O 4 The hollow carbon nano-ring composite material is used as the cathode of the sodium ion battery, because ZnCo 2 O 4 Good electrochemical activity and good conductivity of the hollow carbon nanoring, and the composite material has high specific capacity and rate capability. Meanwhile, the hollow carbon nanoring has excellent mechanical strength, so that ZnCo is effectively slowed down 2 O 4 Agglomeration problem during continuous charge and discharge cycles, making it excellent in cycle stability.
In order to achieve the purpose, the invention adopts the technical scheme that:
based on ZnCo 2 O 4 The method for preparing the negative electrode material of the sodium ion battery by the hollow carbon nanorings comprises the following steps:
first, preparation of ZnCo 2 O 4 Hollow carbon nano-ring composite material
(1) Hollow carbon nanorings, Co (Ac) 2 ·4H 2 O、Zn(Ac) 2 ·2H 2 O is dissolved in the mixed solution of ethanol and deionized water, wherein, Co (Ac) 2 ·4H 2 O and Zn (Ac) 2 ·2H 2 Molar ratio of O2: 1, Co (Ac) 2 ·4H 2 The concentration of O is 3.2-9.6g/L, Zn (Ac) 2 ·2H 2 The concentration of O is 1.4-4.2 g/L. Then is addedAdding ammonia water, wherein the volume ratio of the ammonia water to the ethanol water mixed solution is 1: 100. Carrying out oil bath reaction at 70-90 ℃ for 16-24h to obtain reaction liquid.
(2) And (2) transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle for hydrothermal reaction at the temperature of 120 ℃ and 180 ℃ for 1-5h, washing the solid product obtained by the hydrothermal reaction with ethanol and water respectively, and drying in vacuum.
(3) Calcining the dried product in the step (2) in protective inert atmosphere at the temperature of 250-450 ℃ for 3-10h to obtain ZnCo 2 O 4 Hollow carbon nanoring composite material.
Second, preparing the cathode material of the sodium-ion battery
ZnCo prepared in the first step 2 O 4 Mixing the hollow carbon nano material, the conductive agent and the binder according to the mass ratio of 8:1:1, and preparing the sodium-ion battery negative electrode material by using water as a solvent. Wherein, ZnCo 2 O 4 The hollow carbon nanoring composite material takes a hollow carbon nanoring as a carrier, and ZnCo is uniformly loaded on the surface of the hollow carbon nanoring 2 O 4 The nano-particles can overcome the problems of large volume expansion and poor intrinsic conductivity of metal oxides in the sodium storage process.
Loading the negative electrode material on a copper foil with the loading amount of 1mg/cm 2 . A sodium ion battery is assembled in a glove box by taking 1.0M sodium perchlorate solution (ethylene carbonate/diethyl carbonate as solvent in a volume ratio of 1:1) as electrolyte
Further, in the mixed solution of ethanol and deionized water in the first step (1), the volume ratio of ethanol to deionized water is 24: 1.
Further, the outer diameter of the hollow carbon nanoring in the first step (1) is 100-300nm, the inner diameter is 50-250nm, and the concentration is 1 g/L.
Further, in the first step (2), the vacuum drying temperature is 60-100 ℃, and the drying time is 10-24 h.
Further, in the first step (3), the inert atmosphere comprises nitrogen and argon.
Furthermore, in the second step, the conductive agent is acetylene black, and the binder is carboxymethyl cellulose.
Based on ZnCo 2 O 4 The application of the hollow carbon nanoring in preparing the negative electrode material of the sodium ion battery is characterized in that when the sodium ion battery is loaded, the negative electrode material is loaded on a copper foil, and the loading amount is 1mg/cm 2 . A sodium ion battery was assembled in a glove box using a 1.0M sodium perchlorate solution as an electrolyte.
Further, the solvent of the sodium perchlorate solution comprises ethylene carbonate and diethyl carbonate, and the volume ratio of the ethylene carbonate to the diethyl carbonate is 1: 1.
The experimental result shows that the invention is 1.0A g -1 Has 430mAh g at current density -1 The reversible specific capacity is maintained to be 340mAh g after 2000 cycles of circulation -1 And has excellent cycle stability. Meanwhile, the glass has excellent rate performance of 0.2, 0.5, 1, 2, 5A g -1 The specific discharge capacity of the alloy is 380 mAh g, 350 mAh g, 300 mAh g, 280 mAh g, 240mAh g -1 。
The invention has the beneficial effects that:
(1) ZnCo prepared by the invention 2 O 4 Hollow carbon nanoring composite material, due to sodium storage active substance ZnCo 2 O 4 The combination of the conductive matrix and the nano carbon material and the unique nano annular structure can provide higher specific capacity when used as a negative electrode material of a sodium ion battery, and show better cycle performance and rate capability in the charging and discharging process.
(2)ZnCo 2 O 4 The conductive metal has rich oxidation-reduction sites, and has a synergistic effect between two different metal ions, thereby showing good conductivity and electrochemical activity.
(3) The hollow carbon nano-ring has excellent mechanical strength, excellent conductivity and chemical stability, which are beneficial to electrochemical performance. Meanwhile, the electrolyte has a larger specific surface area and a hollow structure, so that the electrolyte is more favorable for permeation and transfer. The unique hollow nano-ring structure is beneficial to promoting sodium ion diffusion and preventing nano-particles from agglomerating, so that the charge and discharge performance of the composite material is superior to that of the traditional metal oxide nano-particles.
Drawings
FIG. 1 shows ZnCo obtained in example 1 of the present invention 2 O 4 Scanning electron microscope photos of the hollow carbon nano-ring composite material;
FIG. 2 shows ZnCo obtained in example 1 of the present invention 2 O 4 XRD pattern of the hollow carbon nano-ring composite material;
FIG. 3 shows ZnCo obtained in example 1 of the present invention 2 O 4 The CV curve of the test of the hollow carbon nano-ring composite material as the negative electrode of the sodium-ion battery at the sweep speed of 0.1 mV/s;
FIG. 4 shows ZnCo obtained in example 1 of the present invention 2 O 4 Hollow carbon nanoring composite material, ZnCo 2 O 4 And three materials of the hollow carbon nano ring are respectively used as the electrochemical properties of the cathode of the sodium ion battery: FIG. 4(a) shows a value of 1.0A g -1 Cycling performance at current density; fig. 4(b) is the rate capability at different current densities.
FIG. 5 shows ZnCo obtained in example 1 of the present invention 2 O 4 The negative electrode of sodium ion battery made of hollow carbon nano-ring composite material is 1.0A g -1 Long cycle performance plot at current density.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the following examples.
Example 1:
negative electrode material ZnCo of sodium ion battery 2 O 4 A preparation method of the hollow carbon nanoring comprises the following steps:
(1) weighing 100mg hollow carbon nanoring, 320mgCo (Ac) 2 ·4H 2 O、140mgZn(Ac) 2 ·2H 2 Dissolving O in a mixed solution of 96mL of ethanol and 4mL of deionized water, adding 1mL of ammonia water, and carrying out oil bath at 70 ℃ for 24 h;
(2) transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 5 hours at 120 ℃, fully washing the product for 3 times by using ethanol and water respectively, and carrying out vacuum drying for 10 hours at 100 ℃.
(3) Calcining the dried product of the step (2) for 10 hours at 250 ℃ in a nitrogen atmosphere to obtain ZnCo 2 O 4 Hollow carbon nanoring composite material.
ZnCo prepared by the embodiment 2 O 4 The scanning electron microscope of the hollow carbon nano-ring composite material is shown in figure 1, and the scanning electron microscope shows that the prepared ZnCo is prepared 2 O 4 The hollow carbon nanoring composite material is ZnCo 2 O 4 The nano particles are uniformly distributed on the surface of the hollow carbon nano ring. To ZnCo 2 O 4 XRD analysis is carried out on the hollow carbon nano-ring composite material, as shown in figure 2, and the corresponding ZnCo is displayed at the same time 2 O 4 Standard characteristic diffraction peaks.
ZnCo prepared in this example 2 O 4 The negative electrode material is prepared from the hollow carbon nano-ring composite material, acetylene black and carboxymethyl cellulose according to the mass ratio of 8:1:1, a current collector is a copper foil, 1.0M sodium perchlorate solution (ethylene carbonate/diethyl carbonate as a solvent, the volume ratio is 1:1) is used as electrolyte, and a sodium ion half-cell is assembled in a glove box. The cyclic voltammetry test was performed on a Bio-Logic electrochemical workstation with a voltage window of 0.01-3.0V and a sweep rate of 0.1mV/s, with a distinct characteristic redox peak (see FIG. 3). The electrochemical performance of the battery is tested on a Land CT 2001A type battery test system to obtain ZnCo 2 O 4 The hollow carbon nano-ring composite material is 1.0A g -1 Has 430mAh g at current density -1 The reversible specific capacity of the composite material is obviously superior to that of a single-component hollow carbon nano ring and ZnCo 2 O 4 A material. Meanwhile, in the rate capability, ZnCo 2 O 4 The hollow carbon nano-ring composite material is 0.2, 0.5, 1, 2, 5A g -1 The specific discharge capacity of the lithium ion battery is 380 mAh g, 350 mAh g, 300 mAh g, 280 mAh g and 240mAh g respectively -1 Also obviously superior to single-component hollow carbon nanorings and ZnCo 2 O 4 Material (see fig. 4). Hollow carbon nanorings and ZnCo in terms of long cycle performance 2 O 4 After 2000 cycles, the specific capacity of the material is kept at 340mAh g -1 And has excellent cycle stability (as shown in figure 5).
Example 2:
negative electrode material ZnCo of sodium ion battery 2 O 4 Hollow carbon nano-meterA ring preparation method comprising the steps of:
(1) 100mg of hollow carbon nanoring, 640mgCo (Ac) 2 ·4H 2 O、280mgZn(Ac) 2 ·2H 2 Dissolving O in a mixed solution of 96mL of ethanol and 4mL of deionized water, adding 1mL of ammonia water, and carrying out oil bath at 80 ℃ for 20 h;
(2) transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 3h at 150 ℃, fully washing the product for 3 times by using ethanol and water respectively, and carrying out vacuum drying for 12h at 80 ℃.
(3) Calcining the dried product of the step (2) for 6 hours at 350 ℃ in an argon atmosphere to obtain ZnCo 2 O 4 Hollow carbon nanoring composite material.
ZnCo prepared in this example 2 O 4 The negative electrode material is prepared from the hollow carbon nano-ring composite material, acetylene black and carboxymethyl cellulose according to the mass ratio of 8:1:1, a current collector is a copper foil, 1.0M sodium perchlorate solution (ethylene carbonate/diethyl carbonate as a solvent, the volume ratio is 1:1) is used as electrolyte, and a sodium ion half-cell is assembled in a glove box. The electrochemical performance of the battery is tested on a Land CT 2001A type battery test system to obtain ZnCo 2 O 4 The hollow carbon nano-ring composite material is 1.0A g -1 Has 400mAh g at current density -1 The reversible specific capacity of the resin is kept at 290mAh g after 1000 cycles -1 。
Example 3:
negative electrode material ZnCo of sodium ion battery 2 O 4 A preparation method of the hollow carbon nanoring comprises the following steps:
(1) 100mg of hollow carbon nanoring, 960mgCo (Ac) 2 ·4H 2 O、420mgZn(Ac) 2 ·2H 2 Dissolving O in a mixed solution of 96mL of ethanol and 4mL of deionized water, adding 1mL of ammonia water, and carrying out oil bath at 90 ℃ for 16 h;
(2) transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 1h at 180 ℃, fully washing the product for 3 times by using ethanol and water respectively, and carrying out vacuum drying for 24h at 60 ℃.
(3) Calcining the dried product of the step (2) for 3 hours at 450 ℃ in an argon atmosphere to obtain ZnCo 2 O 4 Hollow carbon nanoA rice-ring composite material.
ZnCo prepared in this example 2 O 4 The negative electrode material is prepared from the hollow carbon nano-ring composite material, acetylene black and carboxymethyl cellulose according to the mass ratio of 8:1:1, a current collector is a copper foil, 1.0M sodium perchlorate solution (ethylene carbonate/diethyl carbonate as a solvent in a volume ratio of 1:1) is used as electrolyte, and a sodium ion half-cell is assembled in a glove box. The electrochemical performance of the battery is tested on a Land CT 2001A type battery test system to obtain ZnCo 2 O 4 The hollow carbon nano-ring composite material is 1.0A g -1 Has 360mAh g under the current density -1 The reversible specific capacity is kept at 240mAh g after 1000 cycles -1 。
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (9)
1. Based on ZnCo 2 O 4 The method for preparing the negative electrode material of the sodium ion battery by using the hollow carbon nanorings is characterized by comprising the following steps of:
first, preparation of ZnCo 2 O 4 Hollow carbon nano-ring composite material
(1) Hollow carbon nanorings, Co (Ac) 2 ·4H 2 O、Zn(Ac) 2 ·2H 2 Dissolving O in mixed solution of ethanol and deionized water, wherein, Co (Ac) 2 ·4H 2 O and Zn (Ac) 2 ·2H 2 Molar ratio of O2: 1, Co (Ac) 2 ·4H 2 The concentration of O is 3.2-9.6g/L, Zn (Ac) 2 ·2H 2 The concentration of O is 1.4-4.2 g/L; adding ammonia water, wherein the volume ratio of the ammonia water to the ethanol water mixed solution is 1: 100; carrying out oil bath reaction at 70-90 ℃ for 16-24h to obtain reaction liquid;
(2) transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle for hydrothermal reaction at the temperature of 120 ℃ and 180 ℃ for 1-5h, washing the solid product obtained by the hydrothermal reaction with ethanol and water respectively, and drying in vacuum;
(3) calcining the dried product in the step (2) in protective inert atmosphere at the temperature of 250-450 ℃ for 3-10h to obtain ZnCo 2 O 4 Hollow carbon nanoring composite material;
second, preparing the cathode material of the sodium-ion battery
ZnCo prepared in the first step 2 O 4 Mixing hollow carbon nano material, conductive agent and binder, and preparing the negative electrode material of the sodium ion battery by using water as a solvent, wherein ZnCo 2 O 4 The hollow carbon nano-ring composite material takes hollow carbon nano-rings as carriers, and ZnCo is uniformly loaded on the surfaces of the hollow carbon nano-rings 2 O 4 A nanoparticle; loading the negative electrode material on a copper foil with the loading amount of 1mg/cm 2 A sodium ion battery was assembled in a glove box using a 1.0M sodium perchlorate solution as an electrolyte.
2. ZnCo-based composition according to claim 1 2 O 4 The method for preparing the sodium ion battery cathode material from the hollow carbon nanorings is characterized in that in the first step (1), the volume ratio of ethanol to deionized water is 24:1 in a mixed solution of ethanol and deionized water.
3. ZnCo-based composition according to claim 1 2 O 4 The method for preparing the sodium ion battery cathode material by the hollow carbon nanoring is characterized in that in the first step (1), the outer diameter of the hollow carbon nanoring is 100-300nm, the inner diameter is 50-250nm, and the concentration is 1 g/L.
4. ZnCo-based composition according to claim 1 2 O 4 The method for preparing the sodium ion battery cathode material by the hollow carbon nanorings is characterized in that in the first step (2), the vacuum drying temperature is 60-100 ℃, and the drying time is 10-24 hours.
5. A method according to claim 1ZnCo 2 O 4 The method for preparing the sodium ion battery cathode material by using the hollow carbon nanorings is characterized in that in the first step (3), inert atmosphere comprises nitrogen and argon.
6. ZnCo-based composition according to claim 1 2 O 4 The method for preparing the sodium ion battery cathode material by the hollow carbon nanorings is characterized in that in the second step, the conductive agent is acetylene black, and the binder is carboxymethyl cellulose.
7. ZnCo-based composition according to claim 1 2 O 4 The method for preparing the negative electrode material of the sodium ion battery by the hollow carbon nanorings is characterized in that in the second step, ZnCo 2 O 4 The mass ratio of the hollow carbon nano material to the conductive agent to the binder is 8:1: 1.
8. ZnCo-based catalyst according to any one of claims 1 to 7 2 O 4 The application of the hollow carbon nanoring in preparing the negative electrode material of the sodium ion battery is characterized in that when the sodium ion battery is loaded, the negative electrode material is loaded on a copper foil, and the loading amount is 1mg/cm 2 (ii) a A sodium ion battery was assembled in a glove box using a 1.0M sodium perchlorate solution as an electrolyte.
9. ZnCo-based composition according to claim 8 2 O 4 The application of the hollow carbon nanoring in preparing the sodium ion battery negative electrode material is characterized in that a solvent of a sodium perchlorate solution comprises ethylene carbonate and diethyl carbonate, and the volume ratio of the ethylene carbonate to the diethyl carbonate is 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210773724.4A CN115036502B (en) | 2022-07-01 | 2022-07-01 | Based on ZnCo2O4Method for preparing negative electrode material of sodium ion battery by hollow carbon nano ring and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210773724.4A CN115036502B (en) | 2022-07-01 | 2022-07-01 | Based on ZnCo2O4Method for preparing negative electrode material of sodium ion battery by hollow carbon nano ring and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115036502A true CN115036502A (en) | 2022-09-09 |
| CN115036502B CN115036502B (en) | 2024-05-07 |
Family
ID=83129414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210773724.4A Active CN115036502B (en) | 2022-07-01 | 2022-07-01 | Based on ZnCo2O4Method for preparing negative electrode material of sodium ion battery by hollow carbon nano ring and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115036502B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116377473A (en) * | 2023-03-17 | 2023-07-04 | 大连理工大学 | Nitrogen-doped hollow carbon nano-ring-loaded metal monoatomic material, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100136431A1 (en) * | 2008-12-02 | 2010-06-03 | Samsung Electronics Co., Ltd. | Anode active material, anode including the anode active material, method of manufacturing the anode, and lithium battery including the anode |
| CN103985858A (en) * | 2014-05-23 | 2014-08-13 | 北京理工大学 | Preparation method of ZnCo2O4 nano-plate serving as lithium ion battery negative electrode material |
| KR20160124964A (en) * | 2015-04-20 | 2016-10-31 | 인하대학교 산학협력단 | Ultra-thin hollow carbon nanospheres for sodium ion storing and manufacturing method thereof |
| CN106887575A (en) * | 2017-03-14 | 2017-06-23 | 深圳先进技术研究院 | A kind of cobalt acid zinc/graphene composite negative pole and preparation method thereof and lithium ion battery |
| CN110817845A (en) * | 2019-11-19 | 2020-02-21 | 厦门大学 | Amorphous hollow carbon nanotube and preparation method thereof |
-
2022
- 2022-07-01 CN CN202210773724.4A patent/CN115036502B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100136431A1 (en) * | 2008-12-02 | 2010-06-03 | Samsung Electronics Co., Ltd. | Anode active material, anode including the anode active material, method of manufacturing the anode, and lithium battery including the anode |
| CN103985858A (en) * | 2014-05-23 | 2014-08-13 | 北京理工大学 | Preparation method of ZnCo2O4 nano-plate serving as lithium ion battery negative electrode material |
| KR20160124964A (en) * | 2015-04-20 | 2016-10-31 | 인하대학교 산학협력단 | Ultra-thin hollow carbon nanospheres for sodium ion storing and manufacturing method thereof |
| CN106887575A (en) * | 2017-03-14 | 2017-06-23 | 深圳先进技术研究院 | A kind of cobalt acid zinc/graphene composite negative pole and preparation method thereof and lithium ion battery |
| CN110817845A (en) * | 2019-11-19 | 2020-02-21 | 厦门大学 | Amorphous hollow carbon nanotube and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116377473A (en) * | 2023-03-17 | 2023-07-04 | 大连理工大学 | Nitrogen-doped hollow carbon nano-ring-loaded metal monoatomic material, preparation method and application thereof |
| CN116377473B (en) * | 2023-03-17 | 2023-11-07 | 大连理工大学 | Nitrogen-doped hollow carbon nano-ring-loaded metal monoatomic material, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115036502B (en) | 2024-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108598390B (en) | Preparation method of positive electrode material for lithium-sulfur battery and lithium-sulfur battery | |
| CN111362254B (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| Gan et al. | One-pot biotemplate synthesis of FeS2 decorated sulfur-doped carbon fiber as high capacity anode for lithium-ion batteries | |
| CN101662022B (en) | Nano coating of negative electrode materials and preparation method of secondary aluminium cell using negative electrode materials | |
| CN106207155B (en) | One kind integrates the nano-hybrid material and preparation method thereof of positive/negative cyclical effect | |
| JP2016540341A (en) | Tungsten material, super battery and super capacitor | |
| Xiang et al. | Synergistic capture and conversion of polysulfides in cathode composites with multidimensional framework structures | |
| CN113410475B (en) | Graphitized carbon layer coated transition metal nanoparticle catalyst and preparation method thereof | |
| CN114400309A (en) | Sodium ion positive electrode material and preparation method and application thereof | |
| CN113517426B (en) | Sodium vanadium fluorophosphate/reduced graphene oxide composite material and preparation method and application thereof | |
| CN101060172B (en) | Nano-sized nickel hydroxide/carbon composite material and its manufacture method and purpose | |
| Li et al. | Butterfly-tie like MnCO3@ Mn3O4 heterostructure enhanced the electrochemical performances of aqueous zinc ion batteries | |
| CN112768840A (en) | Multifunctional diaphragm of lithium-sulfur battery and preparation method thereof | |
| CN104953105B (en) | A kind of lithium ion battery SnOxThe preparation method of/carbon nano tube compound material | |
| Chen et al. | High-performanced flexible solid supercapacitor based on the hierarchical MnCo2O4 micro-flower | |
| Tang et al. | Synthesis of NiS coated Fe3O4 nanoparticles as high-performance positive materials for alkaline nickel-iron rechargeable batteries | |
| CN110120526B (en) | Preparation method and application of transition metal alloy/multi-dimensional carbon-based composite electrode material | |
| CN115732660A (en) | Sodium ion layered oxide positive electrode material coating preparation method | |
| CN109950503B (en) | CoMoOxPreparation method of/carbon/sulfur composite nano material, lithium ion battery cathode and lithium ion half battery | |
| Kong et al. | Constructing hierarchical carbon network wrapped Fe3Se4 nanoparticles for sodium ion storage and hydrogen evolution reaction | |
| CN115036502B (en) | Based on ZnCo2O4Method for preparing negative electrode material of sodium ion battery by hollow carbon nano ring and application thereof | |
| Huang et al. | A multifunctional LaFeO3 nanocages modified separator for propelling polysulfides chemisorption and catalytic conversion in Li-S batteries | |
| CN116632195A (en) | Molybdenum diselenide/carbon electrode material, preparation method thereof and normal/low temperature application | |
| CN115986090A (en) | Nitrogen-doped bismuth/carbon composite microsphere material and preparation method and application thereof | |
| Yu et al. | Design of micro-nanostructured Mn 2 O 3@ CNTs with long cycling for lithium-ion 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 |